JPH04329540A - Photographic processing method - Google Patents

Abstract

PURPOSE:To decrease the volume of the processing liquids to be used by allowing the processing to commonly use the processing liquid of a desilvering stage for a 1st photosensitive material having >=3mol% average content of the AgI of the silver halide emulsion applied on a base and a 2nd photosensitive material having <3mol% average content of the AgI of the silver halide emulsion with good photographic performance. CONSTITUTION:Color paper is processed by supplying respectively at least a part of the bleaching bath 120 and fixer 140 used for processing color negative films to a bleach-fixing tank 22 and fixing tank 23 and introducing the discharge liquid of the fixing tank 23 to the bleach-fixing tank 22 in the desilvering processing to execute stages of bleaching fixing to, for example, the color negative films and bleach-fixing fixing to the color paper.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention is mainly concerned with desilvering of silver halide photosensitive materials (hereinafter sometimes abbreviated as "photosensitive materials" or "sensitized materials") used for photographing and printing. The present invention relates to a photographic processing method in which processing liquids are shared.

0002

BACKGROUND OF THE INVENTION After exposure, silver halide color light-sensitive materials are processed through steps such as color development, desilvering, water washing, and stabilization. A color developer is used for color development, a bleach solution, a bleach-fix solution, and a fixer solution are used for desilvering treatment, tap water or ion exchange water is used for washing, and a stabilizing solution is used for stabilization treatment. The temperature of each processing solution is usually adjusted to 20 DEG to 50 DEG C., and the color photosensitive material is immersed in these processing solutions to be processed.

Color photosensitive materials are broadly divided into color photosensitive materials for photography, typified by color negative film and color reversal film, and color photosensitive materials for printing, typified by color paper, color reversal paper, and color autopositive paper. Ru.

These color photosensitive materials have traditionally been processed only in large-scale photofinishing labs, but with the recent development of small-scale processing systems called minilabs, they are now being processed at photo shops and other stores. It has become to. Since these small-scale processing systems are often installed in small stores and the like, it is especially important that the footprint and required work space be small. For this reason, there is a demand for miniaturization of processing apparatuses such as automatic processors and simplification of processing operations.

On the other hand, in recent years, there has been a demand for environmental conservation and resource saving, and attempts have been made to reduce the amount of processing liquid used and the amount of waste liquid.

One of the techniques to meet these demands is to use a common processing solution or a common processing machine for photosensitive materials for photography and photosensitive materials for printing, and various attempts have been made. There is.

In particular, since the desilvering process involves a large number of steps, it is desirable to share the processing liquid used in this process in order to reduce the amount of processing liquid used, and in fact, various proposals have been made. (Japanese Unexamined Patent Publication No. 2-168253, etc.).

By the way, since color photosensitive materials for photography, such as color negative films, mainly use silver iodobromide emulsions, they are difficult to desilver, and the desilvering steps generally include bleaching, bleach-fixing, and Processes such as fixing or bleaching and bleach-fixing or bleaching and fixing are often employed.

On the other hand, color photosensitive materials for printing, such as color paper, usually employ processes such as bleach-fixing, bleach-fixing, and fixing.

For this reason, when using a common processing solution for both types of photosensitive materials, it is better to reuse the processing solution used for the color photosensitive material for photography as the processing solution for the color photosensitive material for printing, which saves processing chemicals and processing solutions. It is often advantageous in terms of reducing the amount used.

However, the processing solution that has fixing ability after processing color negative film contains halide ions (I-, Br-) etc. eluted from the film, and the solution after processing can be used as is. When color paper is processed, desilvering failure occurs and good photographic performance cannot be obtained.

[0012] In order to easily solve such a problem, the present applicant first proposed a process that has a fixing ability for use on a printing photosensitive material using a washing liquid used for washing at least one of the two photosensitive materials. We have proposed a method of diluting the liquid and eliminating the harmful effects of halide ions (Japanese Patent Application No.
No. 322418).

[0013] Although this method can improve this problem, in general, a processing solution with bleaching ability for processing photographic materials is difficult to desilver photographic materials, so it is difficult to desilver photographic materials. For this reason, when a photosensitive material for printing is processed using a processing solution that has the ability to bleach photographic photosensitive materials, bleaching fog occurs.

[0014]

[Problems to be Solved by the Invention] An object of the present invention is to combine two types of photosensitive materials with different silver iodide contents, such as a combination of a photosensitive material for photography and a photosensitive material for printing, while maintaining good photographic performance. Therefore, it is an object of the present invention to provide a photographic processing method in which a processing solution having a desilvering ability can be used in common for processing, and the amount of the processing solution used can be reduced.

[0015]

[Means for Solving the Problems] Such objects are achieved by the following configurations (1) and (6). The following configurations (2) to (5) are preferable.

(1) After exposing and developing a first silver halide photosensitive material in which the silver halide emulsion coated on a support has an average silver iodide content of 3 mol % or more, A second silver halide emulsion which has been treated with a bleaching solution and then with a fixing solution, while the silver halide emulsion coated on the support has an average silver iodide content of less than 3 mol %. In a photographic processing method in which a photosensitive material is exposed, developed, processed with a processing solution having bleaching ability, and then processed with a fixing solution, the first silver halide photosensitive material is processed with bleaching ability. A first processing tank having a bleaching ability filled with a solution, a first fixing tank filled with a fixing solution, and a second processing tank filled with a processing solution having a bleaching ability for processing the second silver halide photosensitive material. A processing tank having bleaching ability and a second fixing tank filled with a fixing solution are installed, and at least a portion of the processing solution having bleaching ability that has been used to process the first silver halide photosensitive material is transferred to the second bleaching tank. supplying at least a part of the fixing solution that has been used to process the first silver halide photosensitive material to the second fixing tank, and at least part of the fixing solution in the second fixing tank A photographic processing method characterized in that the second silver halide photosensitive material is processed by supplying a portion of the material to the second processing bath having bleaching ability.

(2) The photographic processing method according to (1) above, wherein the first processing liquid having bleaching ability is a bleaching solution, and a bleaching tank is installed as the first processing tank having bleaching ability. .

(3) The processing solution having the first bleaching ability is a bleaching solution and a bleach-fixing solution, and the processing tank having the first bleaching ability includes a first bleaching tank and a first bleach-fixing tank. The photographic processing method described in (1) above, in which a is installed.

(4) The photographic processing method according to (3) above, wherein at least a portion of the first bleach-fix solution is supplied to a second processing tank having bleaching ability.

(5) The above (3) supplying at least a part of the bleach solution in the first bleach tank and at least a part of the fixer solution in the first fix tank to the first bleach-fix tank, respectively. ) or the photographic processing method described in (4).

(6) An anode is disposed in the first treatment liquid having bleaching ability, and a current treatment is performed by an ion exchange method using an anion exchange membrane, or in addition to or in place of this, the first treatment solution is The photographic processing method according to any one of (1) to (5) above, wherein a cathode is disposed in the fixing solution (1), and energization treatment is performed by an ion exchange method using an anion exchange membrane.

[0022]

[Operation] In the present invention, when desilvering a first photosensitive material typified by a photosensitive material and a second photosensitive material typified by a printing photosensitive material, the processing liquid used therein is Commonly used for both types of sensitive materials.

[0023] When the first photosensitive material undergoes the process of bleaching and then fixing, and the second photosensitive material takes the process of bleaching and fixing, the bleaching solution and fixing solution are used after processing the first photosensitive material, respectively. at least a portion of the solution is supplied to a bleach-fixing tank and a fixing tank for the second photosensitive material, respectively, and when processing the second photosensitive material, the fixing solution in the second fixing tank is supplied to the bleach-fixing tank. Therefore, even if a highly active bleaching solution for the first photosensitive material is introduced, it will be diluted by the fixing solution, making it possible to prevent bleach fog from occurring in the second photosensitive material.

[0024] Such an effect can be obtained when the first photosensitive material undergoes the process of bleaching → bleach-fixing → fixing, and the second photosensitive material takes the process of bleach-fixing → fixing. At least a portion of the bleach-fixing solution and fixing solution that will be used later is supplied to a bleach-fixing tank and a fixing tank for the second photosensitive material, respectively.
A similar effect can be obtained when processing a photosensitive material.

[0025] In the above, in the bleach-fixing step of the second photosensitive material, the solution filled in the tank at the start of processing may be used as a bleaching solution.

Further, in the present invention, in the processing of the first sensitive material, an anode is disposed in a processing solution having a bleaching ability, and a cathode is disposed in a processing solution having a fixing ability, particularly a fixing solution. The treatment solutions are suitably combined with each other or with an electrolyte containing an electrolyte or another treatment solution, and energization treatment is carried out by an ion exchange method using an anion exchange membrane, and this is carried out in the same manner as above. Used for processing the second photosensitive material.

As a result, the processing performance of the processing liquid having desilvering ability used for the first photosensitive material is restored, and the photographic performance of the first photosensitive material is improved. The photographic performance of the second photosensitive material is improved by being supplied to the processing tank for the second photosensitive material.

[0028] In the processing of two different types of sensitive materials, the overflow liquid of the processing solution used for processing one of the sensitive materials is used for processing the other sensitive material (Japanese Patent Laid-Open No. 6
No. 2-52549, etc.) are disclosed, but there is no disclosure whatsoever regarding the flow of a processing solution as in the present invention in a processing having desilvering ability.

[0029] As described above, the present invention processes a second photosensitive material using at least a portion of each of the processing liquid and fixing liquid having bleaching ability used in processing the first photosensitive material. It is. At this time, since the processing solution with bleaching ability for the first photosensitive material is highly active, if it is used as it is for processing the second photosensitive material, bleach fog will occur, but this problem can be solved by using a post-bath. The problem was solved by introducing a fixer. Also, the first
The fixing solution used to process the second sensitive material contains halide ions, such as I-, that inhibit fixing, and if used as is for processing the second sensitive material, it will cause fixing failure. This problem is solved by diluting the fixing solution by introducing post-bath wash water.

In the processing of the second photosensitive material, the photographic performance can be further improved by introducing the fixing solution diluted in this manner into the pre-bath processing solution having bleaching ability. Therefore, such a flow of the solution in the desilvering process is unique to the present invention, and in the shared process, the effect of suppressing bleaching fog on the second photosensitive material is brought about only by this configuration. .

[0031]

[Specific Configuration] The specific configuration of the present invention will be explained in detail below.

The first light-sensitive material of the present invention is one in which the silver halide emulsion coated on the support has an average silver iodide content of 3 mol% or more, and is mainly applicable to color light-sensitive materials for photography. However, specific examples thereof include color negative film, color reversal film, and the like.

On the other hand, the second photosensitive material is one in which the average content of silver iodide in the silver halide emulsion is less than 3 mol %, and is mainly a color photosensitive material for printing. Examples include color paper, auto-positive color paper, color reversal paper, color-positive film, and the like.

In the present invention, these first and second
Photosensitive materials can be used in any combination. However, normally, such processing of photosensitive materials is often carried out using a so-called integrated processing device, in which processing sections for processing the first and second photosensitive materials are placed adjacent to each other. In order to share the same liquid, it is preferable to use a combination of processing tanks that have similar overall configurations. Therefore, a combination of color negative film and color paper, color reversal film and color reversal paper, etc. is usually used.

The desilvering treatment step in the present invention is a step of bleaching→fixing or bleaching→bleach-fixing→fixing for the first sensitive material, and a step of bleaching-fixing→fixing for the second sensitive material. Incidentally, at the start of processing of the second photosensitive material, the bleach-fixing step may be substantially a bleaching step.

First, the desilvering process of the first photosensitive material is bleaching→
The case of the fixing process will be explained.

At this time, at least a portion of the bleaching solution used to process the first photosensitive material is transferred to a bleach-fix tank for the second photosensitive material, and at least a portion of the fixing solution used to process the first photosensitive material is transferred to the bleach-fixing tank for the second photosensitive material. The fixing tank for the second photosensitive material is supplied to each fixing tank for processing the second photosensitive material. In the second photosensitive material processing tank, at least a portion of the fixing solution in the fixing tank is supplied to a bleach-fixing tank.

FIG. 1 shows an example of the configuration of an integrated processing apparatus for carrying out such a processing method. FIG. 1 is a plan view schematically showing the tank arrangement.

As shown in FIG. 1, the processing apparatus 1 has a negative processing section 10 that processes color negative film as a first photosensitive material, and a paper processing section 20 that processes color paper as a second photosensitive material. .

The negative processing section 10 includes a color developing tank 11 filled with a color developing solution 110, a bleaching tank 12 filled with a bleaching solution 120, a fixing tank 14 filled with a fixing solution 140, and a water washing tank according to the processing process of color negative films. First and second washing tanks 15 and 16 each filled with water W, and a stabilizing liquid 170
A stabilization tank 17 filled with .

On the other hand, the paper processing section 20 includes a color developing tank 21 filled with a color developing solution 210, a bleach-fixing tank 22 filled with a bleach-fixing solution 220, and a fixing tank filled with a fixing solution 230 according to the color paper processing process. Tank 23, first to third washing tanks 24, 25, 2 each filled with washing water W
6 is installed.

In the bleaching tank 12 and the bleach-fixing tank 22 of the negative processing section 10 and the paper processing section 20, the bleaching tank 12 is replenished with a bleaching solution replenisher as shown by the arrow in the figure, and the discharged liquid due to the overflow etc. is removed from the paper. It is designed to flow into a bleach-fixing tank 22 of the processing section 20. In addition, the fixing tank 14
In the fixing tank 23, the fixing tank 14 is replenished with a fixing solution replenisher, as indicated by the arrow in the figure, and the liquid discharged from the overflow or the like flows into the fixing tank 23 of the paper processing section 20.

In this manner, since it is only necessary to replenish the processing liquid from the negative processing section 10, it is possible to reduce the amount of replenishment of processing liquid in the desilvering processing step.

Further, in the paper processing section 20, the fixing tank 2
The liquid discharged from the overflow of No. 3 flows into the bleach-fixing tank 22 at the front. Furthermore, the liquid discharged from the overflow of the first washing tank 24 flows into the fixing tank 23 in the front.

[0045] By adopting such an inflow method,
The fixer 230 for color paper is diluted with washing water W, and the fixer 14 is diluted by the processing of the color negative film.
Halide ions such as I- eluted in fixer 1
Even if it is introduced into the fixing liquid 230 together with the discharged liquid of 40, its influence is reduced, and it is possible to prevent the occurrence of fixing defects on color paper.

Furthermore, in the bleach-fix solution 220, the discharged liquid of the highly active bleach solution 120 for color negatives is introduced, but by introducing the fix solution 230, the activity of the bleach solution 120 is reduced, and the processing of color paper is It becomes suitable for
It is possible to prevent the occurrence of bleaching fog.

Note that the bleach-fixing tank 2 of the paper processing section 20
The processing liquid filled in Step 2 at the start of running does not necessarily have to be a bleach-fixing solution, but may be a bleaching solution.

In the negative processing section 10 and the paper processing section 20, in the washing tanks 15 and 16 and the washing tanks 24, 25 and 26, the water is replenished from the washing tank 16 or 26 at the last stage and sequentially flows into the washing tank at the previous stage. A multistage countercurrent method is adopted. Thereby, the washing efficiency in each processing section 10, 20 can be improved, and the amount of replenishment of washing water W can be reduced. In addition, the first washing tank 15 of the negative processing section 10
The liquid discharged from the overflow etc. is transferred to the paper processing section 2.
The liquid discharged by overflow of the first washing tank 24 flows into the fixing tank 23.

[0049] This also makes it possible to reduce the amount of replenishment of the washing water W, and to reduce the amount of water used in the first washing tank 15 for color negatives.
Even if the discharged liquid flows into the first washing tank 24 for color paper, the color paper will not be washed improperly.

Next, the desilvering process of the first photosensitive material is bleaching →
A case where the process is bleach-fixing → fixing will be explained.

At this time, at least a portion of the bleach-fixing solution used to process the first photosensitive material is transferred to a bleach-fixing tank for the second photosensitive material, and at least a portion of the fixing solution used to process the first photosensitive material is transferred to a bleach-fixing tank for the second photosensitive material. Second
The second photosensitive material is processed by supplying the second photosensitive material to the fixing tank for the photosensitive material. In the second photosensitive material processing tank, at least a portion of the fixing solution in the fixing tank is supplied to a bleach-fixing tank.

FIG. 2 shows an example of the configuration of an integrated processing apparatus for carrying out such a processing method. FIG. 2 is a plan view schematically showing the tank arrangement.

As shown in FIG. 2, the processing apparatus 2 differs from the one shown in FIG. 1 in that the structure of the desilvering tank of the negative processing section 10 is changed according to the desilvering processing step, and furthermore, the processing apparatus 2 is different from the one shown in FIG. This is a configuration in which the method of flowing liquid from the section 10 to the paper processing section 20 is slightly changed.

That is, in the negative processing section 10, the bleaching solution 1
20, a bleach-fix tank 13 filled with a bleach-fix solution 130, and a fix tank 14 filled with a fix solution 140.
is installed. Then, liquid discharged from the overflow of the bleach-fixing tank 13 of the negative processing section 10 flows into the bleach-fixing tank 22 of the paper processing section 20, and liquid discharged from the overflow of the fixing tank 14 flows into the fixing tank 23. It is now possible to do so.

Further, in the negative processing section 10 , the liquid discharged from the overflow of the bleach tank 12 and the liquid discharged from the overflow of the fixing tank 14 flow into the bleach-fix tank 13 .

As shown by the arrow in the figure, replenishment is carried out in the negative processing section 1.
Since the bleaching tank 12 and the fixing tank 13 of 0 are only used, the amount of replenishment can be reduced.

In the bleach-fix tank 13 of the negative processing section 10, the liquid initially filled in the tank may be a bleach-fix solution prepared by mixing the bleach solution 120 and the fix solution 140.

Also in the configuration of FIG. 2, the paper processing section 2
0, the washing water W in the first washing tank 24 is introduced into the fixing liquid 230, and the effect obtained by diluting the fixing liquid 230, and the effect obtained by introducing the fixing liquid 230 into the bleach-fixing liquid 220. The effects and the like are the same as those in FIG.

In the present invention, an electrode may be disposed in a processing solution having a desilvering ability for the first sensitive material, and electrical treatment may be performed by an ion exchange method using an anion exchange membrane. Thereby, the processing performance of each processing liquid in the desilvering step can be further improved. Specifically, among the processing solutions for the first sensitive material, the anode is placed in a processing solution having a bleaching ability, and the cathode is placed in a processing solution having a fixing ability, particularly a fixing solution. and these treatment solutions are brought into contact with each other through an anion exchange membrane, or each of these treatment solutions is brought into contact with an electrolytic solution containing an electrolyte or another treatment solution through an anion exchange membrane. However, the counter electrodes of the electrodes are immersed in these liquids, and electricity is applied to each pair of electrodes to process the first sensitive material.

FIG. 3 shows an example of the configuration of such a processing device. FIG. 3 is a plan view schematically showing the tank arrangement. Further, the processing device 3 in FIG. 3 is the same as that shown in FIG. 1, but employs the above-described energization method.

Therefore, the processing apparatus 3 has a structure in which the bleaching tank 12 and fixing tank 14 of the negative processing section 10 are changed from the one shown in FIG. That is, in the adjacent bleaching tank 12 and fixing tank 14, the partition wall that partitions the bleaching solution 120 and the fixing solution 140 is configured with an anion exchange membrane A1,
The anode 32 is immersed in a bleach solution 120, and the cathode 31 is immersed in a fixer solution 140, respectively, so that both electrodes can be energized.

[0062] At this time, it is preferable that the current be applied during the process. That is, it may be done at the same time as the signal to start processing the photosensitive material is received, or after a predetermined period of time has elapsed, and the energization may be stopped at the end of the processing.

[0063] In addition, when energizing, the current density is 0.02 to 3A.
/dm2, preferably 0.05-1.2A/dm2
It is sufficient to apply a voltage so that The applied voltage varies depending on the liquid used, the form of the processing equipment, the distance between the electrodes, the properties and type of the diaphragm, but conceptually it is 0.05 to 100V.
, preferably 0.1 to 10V.

The configuration of FIG. 3 provides the same effect as that of FIG. 1. Furthermore, by applying electricity, the bleaching solution 12
0, the processing performance is recovered in the fixer 140. In the fixing solution 140, the fixing power of the fixing agent is restored, halide ions are transferred to the bleaching solution 120 and removed, and furthermore, the formation of sulfides derived from the fixing agent and the deterioration of the preservative are prevented. . On the other hand, in the bleaching solution 120, halide ions migrate from the fixing solution 140, so there is no need to add new halide ions, and the oxidizing power of the bleaching agent is also restored. Furthermore, since H+ is generated by the electrode reaction, an increase in pH caused by the color developer 110 of the photosensitive material is suppressed.

In this way, not only the desilvering performance is improved in the negative processing section 10, but also the bleaching solution 120 and the fixing solution 140 with improved processing performance can be introduced into the paper processing section 20. Desilvering performance is also improved in the processing section 20. In particular, the amount of halide ions present in the fixing tank 23 is significantly reduced to the point where it is not necessary to dilute it with the washing water W.

Further, a processing apparatus employing the above-described energization method may have the configuration shown in FIG. 4. FIG. 4 is a plan view showing the tank arrangement. Further, the processing device 4 in FIG. 4 employs the above-described energization method in the device shown in FIG. 2.

Therefore, the processing apparatus 4 has a structure in which the bleaching tank 12 and fixing tank 14 of the negative processing section 10 are changed from the one shown in FIG. That is, a liquid tank 41 filled with an electrolyte 410 and a fixing tank 14 are located adjacent to the bleach tank 12.
A liquid tank 42 filled with an electrolytic solution 420 is installed adjacent to each of the bleaching tank 12 and a liquid tank 41.
The partition wall separating the fixing solution 140 and the electrolytic solution 410 is formed by an anion exchange membrane A2, and the partition wall partitioning the fixing solution 140 and the electrolytic solution 420 is formed by an anion exchange membrane A3. The cathodes 33 were immersed in pairs, and the cathodes 35 were immersed in the fixing solution 140, and the anodes 36 were immersed in pairs in the electrolyte 420, so that each pair of electrodes could be energized. It is something.

The energization at this time may be the same as that shown in FIG. 3.

The configuration of FIG. 4 provides the same effect as that of FIG. 2. Furthermore, similar to the one in FIG. 3, a bleaching solution 120,
The processing performance of the fixing solution 140 and the processing performance of the bleach-fixing solution 130 are restored, and the effect is obtained by supplying a solution with better performance to the paper processing section 20.

In the present invention, the cathode used when applying the current method may be any electrical conductor or semiconductor that can withstand long-term use, such as stainless steel, aluminum, silver, nickel, copper, or zinc. , brass, titanium and the like, with stainless steel being particularly preferred. The anode may be made of an insoluble material and an electrical conductor, and specific examples thereof include carbon (graphite), lead dioxide, platinum, gold, and titanium steel, and in some cases, stainless steel may be used. The shape of both electrodes is preferably a plate shape, a meshed plate shape, or a plate shape with projections so that they can be easily installed in the tank. The size may be appropriately selected depending on the tank capacity.

Any anion exchange membrane may be used as long as it selectively allows anions to pass therethrough, and commercially available membranes can be used as they are.

As described above, as an anion exchange membrane, Se
lemion AWV/AMR (manufactured by Asahi Glass), Acip
lex A201, A172 (manufactured by Asahi Kasei), Neos
epta AM-1~3 (manufactured by Tokuyama Soda), Ionac
MA-3148 (manufactured by Ionac Chemicals), NeptonAR103PZL (manufactured by Ionics)
In particular, in the present invention, Br-
For the purpose of permeation of halide ions such as
Selmion A selectively transmits valent anions
SV/ASR (manufactured by Asahi Glass), Neosepta AF
It is preferable to use those commercially available under trade names such as N-7 and Neosepta ACS (manufactured by Tokuyama Soda).

[0073] In the present invention, the above-mentioned anion exchange membrane is a general term for membranes that selectively permeate anions, and in this sense, the anion exchange membrane has a pore size of 0.2 to 20
Porous ceramics of micrometers are also included.

[0074]Although washing water can be used as the electrolyte, a freshly prepared one may also be used.The electrolyte in this case is not particularly limited, and NaCl, KC
1, halides such as LiCl, NaBr, KBr, Kl, sulfates such as Na2SO4, K2SO4, KN
Nitrates such as O3, NaNO3, NH4 NO3,
Carbonates such as Na2 CO3, K2 CO3, NH4
It is preferable to use hydroxides such as OH.

The concentration of the electrolyte in the electrolytic solution at this time may be 0.1 to 30%, preferably 0.5 to 20%.

[0076] The anion exchange membrane may be appropriately selected depending on the electrolyte.

The bleaching solution, bleach-fixing solution and fixing solution used in the present invention will be described below.

Bleaching agents used in the bleaching solution or bleach-fixing solution include, for example, iron (III) and cobalt (III).
), compounds of polyvalent metals such as chromium (VI) and copper (II), peracids, quinones, nitro compounds, etc. 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 -diaminopropanetetraacetic acid,
Aminopolycarboxylic acids such as glycol ether diamine tetraacetic acid or complex salts such as citric acid, tartaric acid, and malic acid; persulfates; bromates; permanganates; nitrobenzenes and the like can be used. Among these, aminopolycarboxylic acid iron(III) complex salts including ethylenediaminetetraacetic acid iron(III) complex salts and persulfates are preferable 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 pH of the bleaching solution or bleach-fixing solution using these iron(III) aminopolycarboxylic acid complex salts is usually 5.5 to 8, but in order to speed up the processing, it can be processed at an even lower pH. .

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

Specific examples of useful bleach accelerators are described in US Pat. No. 3,893,858;
West German Patent No. 1,290,812, JP-A-53-956
No. 30, Research Disclosure No. 17,
Compounds having a mercapto group or disulfide bond described in No. 129 (July 1978), etc.; JP-A-1988-1
Thiazolidine derivatives described in US Pat. No. 40129; thiourea derivatives described in US Pat. No. 3,706,561; iodide salts described in JP-A-58-16235;
Polyoxyethylene compounds described in Japanese Patent Publication No. 748,430; polyamine compounds described in Japanese Patent Publication No. 45-8836;
Bromide ion etc. can be used. Among these, compounds having a mercapto group or a disulfide bond are preferred from the viewpoint of a large promoting effect, and are particularly preferred as described in U.S. Pat. No. 3,893,858.
No., West German Patent No. 1,290,812, Japanese Unexamined Patent Publication No. 1983-9
The compounds described in No. 5630 are preferred. Further preferred are the compounds described in US Pat. No. 4,552,834.

Examples of fixing agents used in bleach-fixing solutions and fixing solutions include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts. The use is common, especially ammonium thiosulfate, which is the most widely used. Further, as the preservative, sulfites, bisulfites, sulfinic acids, or carbonyl bisulfite adducts are preferable.

[0082] In addition to the above, various processing liquids such as color developing solution, washing water, stabilizing liquid, etc. are used in the processing of color sensitive materials, depending on the processing step. Details of these processing solutions, processing conditions, etc., including those mentioned above, can be found in JP-A-63-70857;
Reference can be made to the description in JP-A-1-190889 and the like.

As mentioned above, the first photosensitive material (mainly a photographic photosensitive material) in the present invention has an average silver iodide content of 3 mol% or more, preferably 3 mol% or more.
Silver iodobromide or silver iodochlorobromide emulsions containing 0 mol % or less of silver iodide are used, and silver iodobromide emulsions containing 3 mol % to 25 mol % of silver iodide are particularly preferred.

On the other hand, as mentioned above, the silver halide emulsion of the second light-sensitive material (mainly a light-sensitive material for printing) in the present invention has an average silver iodide content of less than 3 mol %, and a chloride It is preferably a mixed crystal of one or more of silver, silver bromide, and silver chlorobromide.

In particular, silver chlorobromide containing substantially no silver iodide is preferred. Substantially containing no silver iodide means that the content of silver iodide based on the total amount of silver halide is 1 mol% or less, preferably 0.3 mol% or less, and more preferably 0.1 mol% or less. It should contain no more than mol% of silver iodide, most preferably no silver iodide.

[0086] In the present invention, the second
The emulsion for the light-sensitive material is a silver chlorobromide emulsion having a silver bromide content of 10 mol% or more.

When rapid processing is required, silver chlorobromide emulsions with a silver bromide content of 10 mol % or less are preferred, and silver chlorobromide emulsions with a silver bromide content of 3 mol % or less are particularly preferred. More preferably, a silver chloride emulsion having a silver bromide content of 1 mol % or less and substantially containing no silver bromide is more preferred.

In particular, in the present invention, a color paper or the like using a silver chloride emulsion containing substantially no silver bromide is preferably used as the second light-sensitive material.

The present invention is particularly effective when applied to processing in which the above-mentioned sensitive materials are combined. A combination of a color negative film and a color paper made of a silver chloride or silver chlorobromide emulsion having an average silver bromide content of 10 mol % or less is preferred. With such a combination, poor bleaching and bleaching fog are particularly improved.

In the present invention, the average grain size of silver halide grains in a photographic emulsion (grain diameter in the case of spherical or approximately spherical grains, edge length in the case of cubic grains, average grain size based on projected area) ) may have a narrow or wide particle size distribution. The particle size is preferably about 0.01 to 5 μm.

The silver halide grains in the photographic emulsion may have a regular crystal shape such as a cube or an octahedron, or may have an irregular crystal shape such as a spherical shape or a plate shape. or a composite form of these crystal forms. It may also consist of a mixture of particles of various crystalline forms. The silver halide grains may have different phases inside and on the surface, or may consist of a uniform phase. Further, the particles may be particles in which a latent image is mainly formed on the surface, or may be particles in which a latent image is mainly formed inside the particles.

The photographic emulsion used in the present invention is P. Gla
Chimie et Physiqu by fkides
e Photographique (Paul Mo
(Published by Intel Publishing, 1967), G. F. Duffi
Photographic Emulsion C by n
hemistry (The Focal Press
(Published, 1966), V. L. Zelikman e
Making and Coating by tal
Photographic Emulsion (The
Focal Press, 1964). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and any one-sided mixing method, simultaneous mixing method, combination thereof, etc. may be used to form the reaction between the soluble silver salt and the soluble halogen salt. .

In the process of silver halide grain formation or physical ripening, cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or complex salts thereof, rhodium salts or complex salts thereof, iron salts or iron complex salts, etc. may be allowed to coexist. good.

In order to remove soluble salts from the emulsion after precipitation or physical ripening, a Nudel water washing method in which gelatin is gelatinized may be used, and inorganic salts,
Anionic surfactants, anionic polymers (e.g. polystyrene sulfonic acid), or gelatin derivatives (
For example, a sedimentation method (flocculation) using acylated gelatin, carbamoylated gelatin, etc. may be used.

Silver halide emulsions are usually chemically sensitized. For chemical sensitization, for example H. Frieser
Edited by Die Grundlagen der Photo
graphischen Prozesse mit
Silberhalogeniden (Akademi
sche Verlagsgesllschaft.
1968), pp. 675-734, can be used.

The emulsion used in the present invention is usually one that has been subjected to physical ripening, chemical ripening and spectral sensitization. Additives used in such processes are described in Research Disclosure (RD) vol. 176 Ite
m No. 17643 (December 1978) and vol. 187, No. 18716 (1979
(January), and the relevant sections are summarized in the table below.

Known photographic additives that can be used in the present invention are also listed in the above two Research Disclosures, and Table 1 shows where they are listed.

[0098]

[Table 1]

0099

[Examples] The present invention will be specifically explained below with reference to Examples.

Example 1 A color negative film (silver iodobromide emulsion; silver iodide content average 12 mol%; Ag coating amount 4.86 g/m2) described in Example 1 of JP-A-2-139548 was used. , color paper (high silver chloride emulsion; silver bromide content 1 mol %; Ag
A coating amount of 0.89 g/m2) was applied to 5 rolls of color negative film (24 sheets of 135 size) per day and color paper using the integrated processing device shown in Figure 1 in the processing steps shown in Tables 2 and 3. Running treatment was carried out for 3 months at a treatment rate of 1.4 m2 per day.

[0101]

[Table 2]

[0102]

[Table 3]

[0103] In the processing steps shown in Tables 2 and 3, the color developing solution, washing water, and stabilizing solution for color negatives were prepared from Japanese Patent Application Laid-Open No. 2-13
The color developing solution for color paper and the washing water described in Example 3 of Japanese Patent Application Laid-open No. 70857/1980 were used in Example 1 of Japanese Patent Application Laid-open No. 63-70857. The bleaching solution and fixing solution for color negatives shown in Tables 4 and 5 were used, and the mother liquors of the bleach-fixing solution and fixing solution for color paper were shown in Tables 6 and 7, respectively.

[0104]

[Table 4]

[0105]

[Table 5]

[0106]

[Table 6]

[0107]

[Table 7]

[0108] Such processing is referred to as processing 1A.

Further, in Process 1A, the same process was carried out except that the overflow of the fixing tank in the paper processing section was not allowed to flow into the bleach-fixing tank. This is called processing 1B.

Treatments 1A and 1B were examined and evaluated as follows for the occurrence of bleaching fog, defective desilvering, and defective color recovery at the start of treatment and after three months of treatment.

(1) Bleaching and fogging After color development, immersion in 3% H2 SO4 solution for 5 seconds to stop development, and then bleaching and subsequent processing was used as a control (standard), and immersion in 3% H2 SO4 solution. The increase in the minimum density at this time was defined as bleaching fog, and when the increase was 0.02 or more, it was evaluated as occurrence of bleaching fog.

(2) Desilvering failure Silver analysis using fluorescent X-rays revealed that the amount of residual silver was 5 μg/cm2.
The above was evaluated as occurrence of desilvering failure.

(3) Poor color restoration sensitometry The exposed and processed sensitive material is measured for density with red light, then processed again from bleaching solution and measured for density again.
Evaluation was made based on the increase in density due to reprocessing when the red transmission density was 1.2. At this time, if the density increase was 0.1 or more, it was evaluated that color recovery failure occurred. The results are shown in Table 8.

[0114]

[Table 8]

Table 8 shows that in treatment 1A, no bleaching fog occurred on the color paper after the running treatment. On the other hand, it can be seen that in Process 1B, bleaching fog occurs on the color paper.

Furthermore, in Process 1A, there was no occurrence of defective desilvering or defective color restoration, and good photographic performance was obtained. Furthermore, the total replenishment amount in the desilvering process has been reduced by 30% compared to the case where both photosensitive materials are not jointly processed and processed separately as in the past.
% could be reduced.

Example 2 In the process 1A of Example 1, the process shown in FIG. 3 was applied instead of the process shown in FIG. 1, and the same process was carried out.

At this time, molybdenum-containing stainless steel (SUS31) is used as the cathode installed in the fixing tank of the negative processing section.
6 equivalent) sheet [NTK316 manufactured by Nippon Metal Industries Co., Ltd.:
Size 15 cm x 100 cm (wall thickness 1 mm width)] was installed as an anode in the fixing tank.Cresheet made by Kureha Chemical Industry Co., Ltd.: Size 15 cm x 100 cm
m (thickness: 1 mm width)] were used, respectively.

[0119] Further, the anion exchange membrane is Neosept
a AFN-7 (manufactured by Tokuyama Soda) was used.

[0120] The energization conditions were as follows: 1. A voltage of 10 V was applied;
A current of 5A was allowed to flow (current density 0.07A/
dm2). The voltage was applied one minute after receiving the photosensitive material processing signal, and the voltage application was stopped when the photosensitive material processing signal was not received for 20 minutes. Process this 2A
shall be.

It has been found that Process 2A gives results equivalent to or better than Process 1A in terms of bleaching fog, and even better results in terms of occurrence of defective desilvering and defective recoloring.

Example 3 In the process 1A of Example 1, the process shown in FIG. 2 was applied in place of the process shown in FIG. 1, and the same process was carried out.

At this time, the color negative film processing steps were as shown in Table 9.

[0124]

[Table 9]

In the processing steps shown in Table 9, the mother liquor of the bleach-fix solution is a ratio of 15:8 of the bleach solution mother liquor of Table 4 and the fixer solution mother liquor of Table 5.
A mixed solution of No. 5 was prepared. This is referred to as processing 3A.

In Process 3A, the same process was carried out except that the overflow from the fixing tank in the paper processing section was not allowed to flow into the bleach-fixing tank. This is called process 3B.

In Processes 3A and 3B, photographic performance was investigated in the same manner as in Example 1. In Process 3A, Example 1
It showed good results equivalent to those of treatment 1A. Also processing 3B
The results showed the same results as those of Process 1B of Example 1, and there was a problem in terms of bleaching fog.

Furthermore, in Process 3A, the total amount of replenishment in the desilvering step was reduced by 25% compared to the conventional method which has the same meaning as Example 1.
was able to reduce it.

[0129]

According to the present invention, it is possible to carry out processing in which a processing liquid used in the desilvering process is shared in combinations of photosensitive materials for photographing and photosensitive materials for printing. Even in this case, the photographic performance is good. Furthermore, the amount of processing liquid used can be reduced.

[Brief explanation of drawings]

FIG. 1 is a plan view schematically showing a tank arrangement of a processing apparatus used in the present invention.

FIG. 2 is a plan view schematically showing the tank arrangement of the processing apparatus used in the present invention.

FIG. 3 is a plan view schematically showing the tank arrangement of the processing apparatus used in the present invention.

FIG. 4 is a plan view schematically showing the tank arrangement of the processing apparatus used in the present invention.

[Explanation of symbols]

1, 2, 3, 4 Processing equipment 11, 21 Color developing tank 12 Bleaching tank 13, 22 Bleach-fix tank 14, 23 Fixer tank 15, 16, 24-26 Washing tank 17 Stabilization tank 41, 42 Liquid tank 10 Negative processing section 20 Paper processing section 110, 210 Color developer 120 Bleach solution 130, 220 Bleach-fix solution 140, 230 Fixer W Washing water 170 Stabilizer 410, 420 Electrolyte A1-A3 Anion exchange membrane 31, 33, 35 Cathode 32, 34, 36 Anode

Claims (2)

[Claims] Claim 1: A first silver halide emulsion coated on a support in which the average content of silver iodide is 3 mol% or more.
After exposure and development, the silver halide photosensitive material was processed with a processing solution having bleaching ability, and then processed with a fixing solution, while the silver iodide of the silver halide emulsion coated on the support was processed. After exposing and developing the second silver halide photosensitive material having an average content of less than 3 mol%,
In a photographic processing method comprising processing with a processing solution having bleaching ability and then processing with a fixing solution, the first processing having bleaching ability is filled with a processing solution having bleaching ability for processing the first silver halide photosensitive material. A first fixing tank filled with a tank and a fixing solution, a second processing tank filled with a processing solution having bleaching ability for processing the second silver halide photosensitive material, and a second fixing tank filled with a fixing solution. a second fixing tank, and supplying at least a portion of the processing solution having bleaching ability in which the first silver halide photosensitive material was processed to the second processing tank having bleaching ability; supplying at least a portion of the fixer obtained by processing the silver halide photosensitive material to the second fixing tank, and at least a portion of the fixer in the second fixing tank being subjected to the second bleaching process. A photographic processing method, characterized in that the second silver halide photosensitive material is supplied to a tank and processed. 2. An anode is disposed in the first treatment solution having bleaching ability, and a current treatment is performed by an ion exchange method using an anion exchange membrane, or in addition to or in place of this, the first treatment solution is Claim 1: A cathode is disposed in the fixing solution, and energization treatment is performed by an ion exchange method using an anion exchange membrane.
Photo processing method described in.