JPH04331953A - Processing method of silver halide photographic sensitive material and processing device thereof - Google Patents

Abstract

PURPOSE:To eliminate the drawback that stains are generated in non-image parts of images when the finished photographic sensitive material is preserved at and under a high temp. and high humidity as the removal of the developing agent in the course of processing, such as bleaching, is insufficient in the rapid development processing of the silver halide photographic sensitive material and more particularly the rapid development processing of the color photographic sensitive material. CONSTITUTION:This development processing method for the photographic sensitive material and the processing device used therein consist in using >=2 tanks for the course of processing, such as bleaching of the development processing device and more particularly the rapid development processing device for the color photographic sensitive material and executes control in such a manner that the amt. of the residual developing agent upon ending of the processing in the 1st processing tank of the processing tanks is >=1.5 times the amt. of the residual developing agent upon ending of the processing in the final processing tank of the processing tanks.

Description

[Detailed description of the invention]

0001

[Field of Industrial Application] The present invention relates to a wet processing method and processing apparatus for photographic light-sensitive materials, and more specifically, the processed photographic light-sensitive materials have excellent storage stability, and the processing is rapid. The present invention relates to a wet processing method that can be used to process a photographic material, and a novel processing apparatus for photographic materials used in the processing.

0002

BACKGROUND OF THE INVENTION If the developed photographic material is improperly developed, the image area will generally change in tone and density while the developed photographic material is stored. Undesirable stains may occur in the image area, reducing the value of the image.

[0003] In particular, colored stains appearing in non-image areas are noticeable in both negative films and photographic prints.
Significantly reduces image quality. It is known that stains in non-image areas when negative films and prints are stored at high temperatures and high humidity are caused by residues of the developing agent used in the development process due to poor cleaning.

[0004] As a recent trend in the development processing of photographic light-sensitive materials, it is desired that the processing of all light-sensitive materials be simplified and faster. Particularly in the processing of color prints, the conventional bleach-fixing process is typically 45 seconds even in short processing times. The color developing agent (hereinafter simply referred to as the main agent) incorporated into the photosensitive material during the color development process is rapidly removed from the photosensitive material in the bleach-fix processing solution, and furthermore, it is removed from the photosensitive material by washing with water after this processing step. Since the amount of the active ingredient (hereinafter abbreviated as residual active ingredient amount) was reduced, staining of the white background did not become a problem at all.

[0005] Conventionally, color print processing has been accelerated for news purposes, in which case the bleach-fixing process may take less than 45 seconds, but this processing liquid is disposable and is not suitable for general use. Never used. Although this finished press print does not require long shelf life, it was found that there were no problems when it was subjected to storage tests under high temperature and humidity.

[0006] In the case where the bleaching, bleach-fixing and fixing processes in conventional wet development processing of photographic light-sensitive materials have a multi-tank configuration, Japanese Patent Application Laid-Open No. 49-11131
No. 58-105148 and No. 62
No. 91952, etc., all of which relate to replenishment of a processing liquid for controlling desilvering and redox reactions in a photosensitive layer.

That is, in JP-A No. 49-11131, a bleach-fixing bath is divided in the direction of travel of the photosensitive material, and a regenerating solution with a low silver ion content is added from the end of the bath.
This method stabilizes desilvering by lowering the pH at the beginning of the bath and/or adding a reducing agent to lower the oxidizing power.
In the examples, there is no description of the processed sensitive material, but the time for the bleach-fixing process is described as 4 minutes.

[0008] In JP-A-58-105148, the bleach-fixing process consists of at least two processing tanks, and the processing liquid is supplied in a countercurrent manner, with the fixing component being replenished from the developing tank side and the bleaching process being carried out from the washing tank side. Regarding the processing method for improving desilvering by replenishing components and distinguishing the redox function before and after the processing bath, the light-sensitive material in the example uses a silver chlorobromide emulsion, and the processing is not a rapid processing type. do not have.

JP-A No. 62-91952 discloses that when a silver halide color light-sensitive material with a large amount of coated silver or a high silver iodide content is subjected to wet development processing, processing during the bleach-fixing process is disclosed. At least two tanks are used and replenishment is carried out in the countercurrent direction, the processing time is 0.37 minutes or more per 1 g/m2 of coated silver, and the total bleach-fixing time is 30 seconds to 10 seconds.
minutes, the first bleach-fix time is 45 minutes of the total bleach-fix time.
% or less, and its bleach-fixing processing time is 3.
It is stated that desilvering is possible even with low replenishment as long as it is 0 seconds or longer. No mention is made here of residual developing agent.

[0010] Also, in Japanese Patent Application Laid-Open No. 1-267648,
Although a processing tank having a closed multi-chamber type processing chamber that can be applied to each processing step of development processing is described, what is described in the Examples is a water washing step.

[0011] The multi-tank development process mentioned above includes cases in which the bleaching, bleach-fixing, and fixing processes (hereinafter abbreviated as bleaching, etc. process) have a multi-tank configuration. There is. However, in the prior art, increasing the number of baths in processes such as bleaching is a process improvement technique that focuses on desilvering performance, and no attention is paid to the behavior of the main ingredient in the emulsion layer of photographic light-sensitive materials. do not have. This is because in these conventional bleaching processes, by the time desilvering is completed (or the dissolution and removal of silver halide is completed), the amount of the main agent in the photosensitive layer is sufficiently small to be used in the next process. This is because, considering the removal of the main ingredient in step 1, there was no problem with the shelf life of the finished photographic material.

[0012] Conventionally, the effect of accelerating the removal of the main ingredient from the sensitive material is increased by high stirring, high temperature, and long time, and it is thought that increasing the number of processing tanks does not have a great effect. It can be seen that there is almost no benefit from multi-stage processing for the removal of the main drug. [The Chemistry of Cleaning to Maintain and Improve the Quality of Photo Processing in Minilabs]
ashing The Way to ensure
PhotoprocessingQuality of
Minilabs) Iwano et al. (1988) The 5t
h International Symposium
on Photofinishing Technol
ogy, Chicago] From the above, based on the conventional technology, it is not expected that stain generation when finished prints are kept at high temperatures and high humidity will be resolved by multi-tank bleaching and other processes. do not have.

[0013] Furthermore, in the prior art, there is no technology in which processes such as bleaching treatment are carried out in multiple tanks in a rapid processing system. As a recent trend, it has been desired to simplify and speed up the wet development process for all photosensitive materials. This demand is particularly strong for color print photosensitive materials.

[0014] In order to simplify and speed up processing, it is naturally necessary to shorten the processing time of each processing step. In order to shorten this processing time, for example, in the developing process, research should be conducted on factors such as the type of developing agent, its usage amount, and pH, and it will be necessary to quickly achieve high sensitivity, good gradation (color balance), etc. Research has been conducted to obtain high-quality images, and in order to achieve rapid desilvering in processes such as bleaching, the type and amount of bleach used, the pH value of the processing solution, and the types of additives such as preservatives have been investigated. Research has been conducted on the amount of silver used and the amount used, making rapid desilvering possible.

[0015] As the wet development process of photographic light-sensitive materials becomes faster and faster, phenomena that have not been experienced in conventional development processes are becoming apparent. One such phenomenon is that if the main agent is not sufficiently washed out of the photosensitive material during bleaching or other processes, stains may occur in non-image areas when the finished image is stored at high temperatures and high humidity, especially in color. Occurrence of stain on the white background is observed in the print,
A solution to this problem is strongly desired.

In order to realize rapid processing, the developing agent tends to become more hydrophobic during the color development process, and the concentration of the developing agent in the processing solution tends to increase. Based on the phenomenon experienced in the process of rapid processing, even in conventional wet processing processes, such as bleaching, we measured the residual amount of the main ingredient at the end of the process, and compared it with that of the finished photographic material. When compared with the evaluation of the staining phenomenon in non-image areas under high temperature and high humidity conditions, it was found that when developing photographic materials with a large amount of active ingredient residue, stains may occur in non-image areas of finished photographic materials. It has been found.

[0017]

SUMMARY OF THE INVENTION An object of the present invention is to improve the storage stability of finished photographic images that have undergone image processing. In particular, the objective is to eliminate stains that occur in non-printing areas of finished photographic images due to long-term storage at high temperatures and high humidity.

[0018] In any photographic light-sensitive material, the cause of stains that occur in photographic images is largely due to residual residue of the main agent used for development due to poor washing out in the post-development process.

Recently, there has been a strong demand for improvement in color printing materials, in particular for color printing materials, for which there is a strong demand for simple and rapid processing, so as to eliminate insufficient removal of the main agent during the bleaching process and the like during development.

Therefore, the problem of the present invention is to (1) desilver and/or remove silver halide crystals during the wet development process of a silver halide photographic light-sensitive material using a processing solution having a bleaching function and/or a fixing function; After the silver halide photographic light-sensitive material has been developed and dried, the amount of developing agent remaining in the emulsion layer of the silver halide photographic light-sensitive material under processing at the time of completion of processing is determined by To remove dirt to an amount that does not generate dirt even after long-term storage, and to provide an apparatus for carrying out the treatment.

A further object of the present invention is (1) to prevent bleaching and/or
Alternatively, in the fixing process, the amount of developing agent remaining in the emulsion layer of the silver halide color photographic light-sensitive material at the time when desilvering and/or removal of silver halide crystals is completed is determined by controlling the amount of developing agent remaining in the emulsion layer of the silver halide color photographic light-sensitive material during the fixing process. It is an object of the present invention to remove dirt to an amount that does not generate stains even after long-term storage under high humidity, and to provide an apparatus for carrying out the treatment.

[0022] During the wet development process, by using two or more tanks containing the processing liquid in the processing process using a processing liquid having a bleaching function and/or a fixing function, it is unexpectedly possible to improve the quality of the finished image under high temperature and high humidity conditions. It has been found that stains in non-image areas are improved when the image is stored in storage, and as a result of research, the present invention has been arrived at.

[0023]

[Means and Effects for Solving the Problems] The above-mentioned problems of the present invention are as follows: 1) A halogenated compound having at least one process containing a developing agent and having a developing function and at least one process having a bleaching function and/or a fixing function. In a method for processing a silver photographic material, the process having a bleaching function and/or a fixing function consists of at least two tanks having substantially the same function, and the silver halide which has completed the first tank of the process having the same function. A processing method in which the amount of developing agent contained in the photographic light-sensitive material is controlled to be at least 1.5 times the amount of developing agent contained in the silver halide photographic light-sensitive material that has completed the final bath having the same function. or 2) a method for processing a silver halide photographic material having at least one step each of a step containing a developing agent and having a developing function and a step having a bleaching function and/or a fixing function, wherein the bleaching function and/or the fixing function The process comprising at least two tanks having substantially the same function, and the processing time of the process having the same function being controlled to be within 30 seconds.

3) The above problem is solved by the above-mentioned processing method in 1) or 2), in which the silver halide light-sensitive material in the process is This can be better achieved by a method for processing a silver halide photographic material, which is characterized in that it is transferred while immersed in a solution.

4) In a processing apparatus for silver halide photographic materials having at least one process containing a developing agent and having a developing function and at least one process having a bleaching function and/or a fixing function, the bleaching function and/or the fixing function The process having the same function consists of at least two successive tanks having substantially the same function and is equipped with a replenisher supply means, and the developing process contains the photosensitive material that has completed the first tank of the process having the same function. A processing device in which the amount of the main agent is controlled to be at least 1.5 times the amount of the developing agent contained in the photosensitive material that has completed the final bath having the same function. or 5) in a processing apparatus for silver halide photographic materials having at least one process containing a developing agent and having a developing function and at least one process having a bleaching function and/or a fixing function, the bleaching function and/or the fixing function the process comprises at least two consecutive vessels having substantially the same function;
The processing apparatus is further provided with a replenisher supply means, and is controlled so that the processing time of the processing step is within 30 seconds. or 6) In the processing apparatus described in 4) or 5) above, in the process apparatus having a bleaching function and/or fixing function and consisting of at least two consecutive tanks, the silver halide photographic light-sensitive material in the process is 1. A processing apparatus for silver halide photographic materials, characterized in that the silver halide photographic material is transferred while being immersed in a processing liquid. Using this method, the above-mentioned processing methods 1), 2), or 3) were implemented, and the objective could be achieved.

Further, the processing method that more preferably achieves the object of the present invention is as follows: 7) Processing of a silver halide color photographic light-sensitive material having at least one each of a color development process containing a developing agent and a bleaching and/or fixing process. In the method, the bleaching and/or fixing step consists of at least two tanks having substantially the same function, and the processing time of the step is controlled to be within 30 seconds, and the processing method allows the above-mentioned The problem (2) is preferably achieved.

In 1) and 4) of the above methods for solving problems, the amount of developing agent contained in the photosensitive material that has completed the first bath is the amount of developing agent that has been contained in the photosensitive material that has completed the final bath having the function. is preferably 1.5 times or more and 150 times or less,
It is more preferably 1.5 times or more and 45 times or less, and particularly preferably controlled between 1.5 times and 15 times. If the removal of the active ingredient in a tank near the final stage by the processing liquid having this function progresses and the amount of active ingredient becomes extremely small, the magnification of the amount of active ingredient contained in the amount of photosensitive material that has finished the first tank will be It gets expensive.

The equilibrium value of the developing agent in the post-processing solution in the post-development process and in the emulsion layer of the photographic material is determined by the amount of replenisher replenished into the processing tank and the developer carried out by the photographic material from the development process. For example, the Journal of
Journal of Motion Picture and Television Engineers
ture and Television Engi
neers), Vol. 64, pp. 248-253 (May 1955 issue).

It is also possible to actually perform the treatment continuously and determine the amount of the main drug in the treatment solution by liquid chromatography or the like. The volume of the processing solution in the photographic material calculated from the amount of developing agent in the processing solution in the post-development process (processing process with bleaching function, etc.) determined above and the amount of swelling of the emulsion layer of the photographic material during processing. From this, the amount of the main drug per unit volume (equal to the concentration of the main drug in the processing liquid if equilibrium is established) can be calculated.

Directly calculating the concentration of the main agent in the emulsion layer of the photographic material involves removing the developing agent from the emulsion layer of the photographic material at the end of the first bath processing and at the end of the processing of this function using acetic acid. It can be extracted and measured by liquid chromatography.

In the present invention, controlling the amount of the active ingredient in the emulsion layer of the photographic light-sensitive material or in the processing solution during processing means measuring the absorption spectrum specific to the active ingredient in the processing solution.
This includes automatically controlling the amount of the main chemical in the processing solution, such as by blocking the amount of replenisher and the amount of developer brought in at the entrance of the first tank of the processing tank for bleaching, etc. The amount of processing solution brought into the processing tank from the pre-processing tank and the amount of replenisher should be determined in advance, taking into account the type and amount of photographic material to be processed, processing speed, processing agent used, processing conditions, and of course the functions of the processing machine. , controlling the amount of the main chemical in the emulsion layer or processing solution of the photographic light-sensitive material during processing, including the number of processing tanks, the washing after the processing tank, the setting of conditions such as stabilization treatment, etc. means.

[0032] The operation of the present invention will be explained. Wet-type photographic processing is generally carried out for black and white light-sensitive materials in the following steps: development, fixing, and washing.

For color photosensitive materials, the processing steps are as follows depending on the method of bleaching and fixing: color development - bleach fixing - (washing and/or stabilizing bath) color development -
Bleach-fixing - Fixing (washing with water and/or stabilizing bath) Color development - Bleaching - Fixing - (washing with water and/or stabilizing bath)
Color development - bleaching - bleach-fixing - (washing and/or stabilizing bath) Color development - bleaching - bleach-fixing - fixing - (washing and/or stabilizing bath) Color development - fixing - bleaching - fixing - (washing and/or stabilizing bath) ) Color development - fixing - bleach-fixing - (washing with water and/or stabilizing bath) etc. are typical.

The above-mentioned phrase "consisting of at least two tanks having substantially the same function" can be specifically explained using the processing process of the color photosensitive material exemplified above. Bleach-fixing (washing and/or stabilizing bath) means that two or more tanks for carrying out the bleach-fixing process are installed in succession.

In addition, a processing method has been proposed in which an attempt is made to wash the developer or color developer with running water immediately after completion of development or color development in order to prevent the developer from being brought into the next process. Since people started to value uniformity, this process has become a disturbance factor, and installing equipment for this process complicates the equipment and takes time in terms of processing management. How is it not done?

Therefore, in both silver halide black-and-white photographic materials, silver halide color photographic materials, and both negative and positive photographic materials, the first step is to undergo a development process involving a developing agent (color development process). )
As a post-process, a treatment having a bleaching function and/or a fixing function is performed.

Let us consider the process of removing silver (and/or silver halide) and the process of removing the main agent from the photographic material during the process of performing the above-mentioned bleaching process (or process of bleaching function, etc.).

[0038] In cases where the entire process of conventional wet development processing takes more than 3 minutes, and the process including bleaching etc. takes more than 45 seconds, the processing process such as bleaching is particularly difficult. One bath is sufficient except for the process of promoting silver, and in that case, the amount of the active ingredient in the photographic material undergoing processing will reach equilibrium with the active ingredient concentration in the processing solution, such as bleaching.
In addition, the amount of the main agent in the photographic emulsion layer is determined to be an amount that does not cause stains in the non-image areas of the finished image even when stored in high temperature and high humidity after the development process is completed (this amount of the main agent is determined as " at least after the rinsing process.

With the recent demand for rapid wet development processing methods, desilvering and/or silver halide removal (hereinafter simply abbreviated as desilvering) is the main purpose of processing processes such as bleaching.
As technology advances, the time required for desilvering has been shortened, and once desilvering has been substantially completed, the amount of main agent in the emulsion layer of the photographic material being processed (at this time, bleaching, etc.) is not necessarily required. There have been cases in which the concentration of the active ingredient in the treatment solution does not necessarily reach equilibrium) and does not reach an "acceptable" amount.

Here, the lower limit of the amount of the active ingredient that remains in the emulsion layer of the photographic light-sensitive material and causes staining in non-image areas when the finished image is stored under high temperature and humidity conditions, ie The upper limit of the "acceptable amount" varies depending on factors such as the type of photographic material in question, the type of developing agent, test conditions, and remaining chemicals other than the active agent.

[0041] The residual amount of the active ingredient in the finished image in excess of the "acceptable amount" is a phenomenon often encountered in rapid processing processes, but it can also occur in normal development processing processes that require longer processing times. . This is because, depending on the type of developing agent used, the structure of the emulsion layer, etc., it may be difficult for the developing agent to flow out into a processing solution such as bleaching.

However, except for such special cases, increasing the number of processing tanks for bleaching, etc. in the normal development processing process is ineffective, and only complicates the structure of the processing machine and increases costs. be.

Unlike the water washing process, the bleaching process has a unique function such as bleaching, so the processing time of this process cannot be extended just for the purpose of removing the main agent. By prolonging processes such as bleaching too much,
If chemicals in the processing solution that are not consumed by the reaction remain in the emulsion layer, they can also cause other quality degradation in the finished image.

In such a situation, if the time required for desilvering etc. is fixed and the number of processing tanks for bleaching etc. is increased to two or more, then the processing solution having the function of bleaching etc. is replenished from downstream. Although the concentration of the active ingredient in the processing liquid in the first tank may increase due to the developer brought in by the photographic material being processed, the concentration of the active ingredient in the processing liquid in the second tank and below will continue to decrease. On the other hand, processing components with bleaching functions, etc. become more similar to fresh liquid, so at the end of the first tank of a two-tank configuration (because sufficient processing time has passed, the concentration of each component in the processing process reaches a steady state). By the way, the level of desilvering etc. and the residual level of the main agent are higher than the level of desilvering etc. and the residual level of the main agent for a considerable time in the case of the conventional one-layer process, but In other words, at the final stage of the bleaching process, the desilvering level is almost zero, and the active ingredient concentration level is reduced to an acceptable level or very close to it. It is the function of the present invention that the objective is achieved.

As mentioned above, the allowable concentration of the developing agent at the end of the post-development process, that is, the bleaching process, etc., depends on the type of photographic material, the type of developing agent, and the bleaching process. Conditions for processing and washing processes,
It varies depending on factors such as remaining chemicals other than the main drug.

In addition, even if the post-color development process (in most cases, the post-process is a bleach-fixing process) for silver halide color photographic materials requires two or more tanks, increasing the complexity of the equipment, it is possible to It is possible to remove silver and silver halide, and no stains appear on the white background of the finished image, so it is recognized that the countermeasure has sufficient significance. Such measures (increasing the number of tanks in processes such as bleaching) are taken when the processing speed is increased so that the processing process takes less than 30 seconds, and processing processes that do not reach this processing speed are subject to bleaching. The necessity of using two tanks for the fixing process was not recognized.

A processing tank is disclosed in which a silver halide photographic light-sensitive material can be transferred with its photosensitive layer immersed during processing. For example, Japanese Patent Application Laid-Open No. 2-205846 discloses a plurality of cleaning chambers sequentially connected by narrow passages,
A device is described in which a photographic material can be conveyed so as to sequentially pass through each of the cleaning chambers in an immersed state. This device is also equipped with a device that can shield the passageway when no photographic material is passing through, and a
It is designed to supply fresh cleaning liquid and to allow the cleaning liquid to flow in the opposite direction to the photographic material.

[0048] The apparatus is used as an apparatus suitable for the present invention by using a processing tank divided into a plurality of sections having the narrow passage and a shielding means in the middle thereof, and performing processing using a bleaching liquid or a processing liquid instead of the washing liquid. It was found that suitable results could be obtained.

In the above sense, in the method and apparatus of the present invention, it is preferable to replenish the tank with a processing liquid having a function such as bleaching from the rear of the final tank, and discard the liquid from the first tank. .

The time required for the entire process of rapid development of silver halide color light-sensitive materials is 3 minutes or less, preferably 2 minutes and 30 minutes.
It is particularly preferably 2 minutes or less. After processes such as bleaching,
The time required to finish washing with water is 25 seconds to 70 seconds, and the time for bleaching etc. is 0.25 to 2 times the washing time. Further, the bleaching process is optional as long as it lasts for 4 seconds or more.

The light-sensitive material in the present invention may be any light-sensitive material that uses a processing liquid, such as black-and-white photographic materials for printing, medical use, and general use, and color photographs such as color negative films, color reversal films, and color papers. There are photosensitive materials. The processing of the present invention can process color prints by taking advantage of speed, and can be applied to intelligent color hard copy processing where speed is more desirable.

In particular, in an embodiment in which the present invention is applied to intelligent color hard copies, it is preferable to carry out scanning exposure using high-density light such as a laser (for example, a semiconductor laser) or a light emitting diode.

Silver halides used in the light-sensitive material according to the present invention include silver chloride, silver bromide, (iodine) silver chlorobromide,
Silver iodobromide etc. can be used, but especially for the purpose of rapid processing, silver chloride containing substantially no silver iodide can be used.
It is preferred to use silver chlorobromide or silver chloride emulsions with a mole % or more, more preferably 95% or more, particularly 98% or more.

[0054] In the photosensitive material according to the present invention, in order to improve image sharpness, etc., the hydrophilic colloid layer is added to the hydrophilic colloid layer described in European Patent No. 27 of EP 0,337,490A2.
Adding dyes that can be decolorized by processing (especially oxonol dyes) described on pages 76 to 76 so that the optical reflection density at 680 nm of the light-sensitive material is 0.70 or more, or improving the water resistance of the support The resin layer contains 12% by weight or more (more preferably 14% by weight) of titanium oxide that has been surface-treated with a di- to tetrahydric alcohol (for example, trimethylolethane), etc.
(above)) is preferably included.

Further, in the light-sensitive material according to the present invention, it is preferable to use a color image preservation improving compound as described in European Patent EP 0,277,589A2 together with a coupler. Particularly preferred is the combination with a pyrazoloazole coupler.

That is, a compound that chemically bonds with the aromatic amine developing agent remaining after color development processing to produce a chemically inert and substantially colorless compound and/or an aroma remaining after color development processing. The use of a compound that chemically combines with the oxidized form of a group amine color developing agent to form a chemically inert and substantially colorless compound may be used simultaneously or singly, for example, to reduce the amount remaining in the film during storage after processing. This is preferable in order to prevent the generation of stains and other side effects due to the formation of color pigments due to the reaction between the color developing agent or its oxidized product and the coupler.

[0057] The photosensitive material according to the present invention also has a preventive agent as described in JP-A No. 63-271247, in order to prevent various types of mold and bacteria that propagate in the hydrophilic colloid layer and cause image deterioration. It is preferable to add a fungicide.

The support used in the light-sensitive material according to the present invention may be a white polyester support for display purposes or a support on the side having a silver halide emulsion layer on which a layer containing a white pigment is provided. A support may also be used. In order to further improve sharpness, it is preferable to coat an antihalation layer on the side on which the silver halide emulsion layer is coated or on the back side of the support. In particular, the transmission density of the support was set to 0.3 so that the display can be viewed with both reflected and transmitted light.
It is preferable to set it in the range of 5 to 0.8.

The photosensitive material according to the present invention may be exposed to visible light or infrared light. The exposure method may be low illuminance exposure or high illuminance short time exposure, and in the latter case in particular, a laser scanning exposure method in which the exposure time per pixel is shorter than 10 -4 seconds is preferred.

The exposed photosensitive material may be subjected to color development processing, but for the purpose of rapid processing, it is preferable to carry out bleach-fixing processing after color development. In particular, when the high silver chloride emulsion is used, the pH of the bleach-fix solution is preferably about 7 or less, more preferably about 6.5 or less, for the purpose of promoting desilvering.

Silver halide emulsion and other materials (additives, etc.) and photographic constituent layers (layer arrangement, etc.) applied to the light-sensitive material according to the present invention, and the processing method applied to process this light-sensitive material As processing additives, the following patent publications, especially European patent EP 0,355,660A2
Those described in the specification of Japanese Patent Application No. 1-107011 are preferably used.

[0062]

[Table 1]

[0063]

[Table 2]

[0064]

[Table 3]

[0065]

[Table 4]

[0066]

[Table 5] Also, as a cyan coupler, JP-A-2-33144
In addition to the diphenylimidazole cyan coupler described in the publication, the 3-hydroxypyridine cyan coupler described in European Patent EP 0,333,185A2 (in particular, 4 equivalents of coupler (42) listed as a specific example) Particularly preferred are couplers with a chlorine-leaving group to make them two equivalents, couplers (6) and (9), and cyclic active methylene cyan couplers described in JP-A-64-32260 (especially preferred). Particular preference is given to the couplers examples 3, 8, 34 listed by way of example).

In the present invention, a color developer or a black and white developer is used as the developer. The color developer used in the present invention contains a known aromatic primary amine color developing agent. Preferred examples are p-phenylenediamine derivatives, representative examples of which are shown below, but are not limited thereto.

D-1 N,N-diethyl-p-phenylenediamine D-2 4-amino-N,N-diethyl-3-methylaniline D-3 4-amino-N-(β-hydroxyethyl)
-N-Methylaniline D-4 4-Amino-N-ethyl-N-(β-hydroxyethyl)aniline D-5 4-Amino-N-ethyl-N-(β-hydroxyethyl)-3-methylaniline D -6 4-Amino-N-ethyl-N-(3-hydroxypropyl)-3-methylaniline D-7 4-amino-N-ethyl-N-(4-hydroxybutyl)-3-methylaniline D-8 4-Amino-N-ethyl-N-(β-methanesulfonamidoethyl)-3-methylaniline D-9
4-amino-N,N-diethyl-3-(β-hydroxyethyl)aniline D-10 4-amino-N-ethyl-N-(β-methoxyethyl)-3methyl-aniline D-11 4-amino- N-(β-ethoxyethyl)
-N-Ethyl-3-methylaniline D-12 4-Amino-N-(3-carbamoylpropyl-N-n-propyl-3-methylaniline D-13
4-amino-N-(4-carbamoylbutyl-N-
n-propyl-3-methylaniline D-14 N-(
4-Amino-3-methylphenyl)-3-hydroxypyrrolidine D-15 N-(4-amino-3-methylphenyl)
-3-(hydroxymethyl)pyrrolidine D-16 N-(4-amino-3-methylphenyl)
-3-pyrrolidinecarboxamide Among the above p-phenylenediamine derivatives, particularly preferred are exemplary compounds D-5, D-6, D-7, D-8 and D-
It is 12. Further, salts of these p-phenylenediamine derivatives with sulfates, hydrochlorides, sulfites, naphthalenedisulfonic acid, p-toluenesulfonic acid, etc. may also be used. The amount of the aromatic primary amine developing agent used is preferably 0.002 mol to 0.2 mol per liter of developer,
More preferably 0.005 mol to 0.15 mol, still more preferably 0.01 mol to 0.15 mol.

In practicing the present invention, it is preferred to use a developer substantially free of benzyl alcohol. Here, "substantially not containing" preferably means 2
The benzyl alcohol concentration is less than or equal to milliliter/liter, more preferably less than 0.5 milliliter/liter, and most preferably, it contains no benzyl alcohol at all.

It is more preferable that the developing solution used in the present invention does not substantially contain sulfite ions. The sulfite ion functions as a preservative for the developing agent, and at the same time has the effect of dissolving silver halide and reacting with the oxidized product of the developing agent to reduce the dye formation efficiency. This kind of effect is
This is presumed to be one of the causes of increased fluctuations in photographic characteristics due to continuous processing. Here, "substantially not containing" means preferably having a sulfite ion concentration of 3.0 x 10-3 mol/liter or less, and most preferably not containing any sulfite ions. However, in the present invention, a very small amount of sulfite ion used to prevent oxidation in a processing agent kit in which the developing agent is concentrated before being mixed into a solution for use is excluded.

The developer used in the present invention preferably contains substantially no sulfite ions, and more preferably substantially no hydroxylamine. This is because hydroxylamine functions as a preservative for the developing solution and also has silver developing activity itself, and it is believed that fluctuations in the concentration of hydroxylamine greatly affect photographic properties. Here, "substantially not containing hydroxylamine" preferably means 5.0 x 10-3
hydroxylamine concentration less than or equal to mol/liter;
Most preferably it does not contain any hydroxylamine.

It is more preferable that the developer used in the present invention contains an organic preservative instead of the hydroxylamine or sulfite ion. The term "organic preservative" as used herein refers to any organic compound that reduces the rate of deterioration of an aromatic primary amine color developing agent when added to a processing solution for a color photographic light-sensitive material. That is, they are organic compounds that have the function of preventing color developing agents from being oxidized by air, among others, hydroxylamine derivatives (excluding hydroxylamine; the same shall apply hereinafter), hydroxamic acids, hydrazines,
Hydrazides, phenols, α-hydroxyketones, α-aminoketones, sugars, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, condensed rings Formula amines are particularly effective organic preservatives. These are JP-A-63-4235 and JP-A-63-30.
No. 845, No. 63-21647, No. 63-44655
No. 63-53551, No. 63-43140, No. 63-56654, No. 63-58346, No. 63-
No. 43138, No. 63-146041, No. 63-44
No. 657, No. 63-44656, U.S. Patent No. 3,61
No. 5,503, No. 2,494,903, Japanese Unexamined Patent Publication No. 5
It is disclosed in various publications or specifications such as No. 2-143020 and Japanese Patent Publication No. 48-30496.

[0073] As other preservatives, JP-A-57-441
48 and 57-53749, salicylic acids as described in JP-A-59-180588, alkanolamines as described in JP-A-54-3532, JP-A-56- Polyethyleneimines described in Publication No. 94349, U.S. Pat. No. 3,746,544
If necessary, aromatic polyhydroxy compounds described in the specification and the like may be contained. In particular, it is preferable to add alkanolamines such as triethanolamine, dialkylhydroxylamines such as diethylhydroxylamine, hydrazine derivatives, or aromatic polyhydroxy compounds.

Among the above-mentioned organic preservatives, hydroxylamine derivatives and hydrazine derivatives (hydrazines and hydrazides) are particularly preferred, and details thereof can be found in JP-A-1-97953, JP-A-1-186939, and JP-A-1-1-1.
It is described in No. 186940, No. 1-187557, etc.

Further, it is more preferable to use the above-mentioned hydroxylamine derivative or hydrazine derivative in combination with amines from the viewpoint of improving the stability of the color developer and further improving the stability during continuous processing.

[0076] As the above-mentioned amines, Japanese Patent Application Laid-Open No. 63-2
Cyclic amines such as those described in JP-A No. 39447, amines such as those described in JP-A-63-128340, and other amines such as those described in JP-A-1-186939 and JP-A-1-187.
Examples include amines such as those described in Japanese Patent No. 557.

In the present invention, it is preferred that the color developer contains 3.5 x 10 -2 to 1.5 x 10 -1 mol/liter of chlorine ions. Particularly preferably, 4×
It is 10-2 to 1×10-1 mol/liter. If the chloride ion concentration is more than 1.5 x 10-1 mol/liter, it has the disadvantage of retarding development, which is not preferable in achieving the object of the present invention, which is rapid development and a high maximum concentration. Also, if it is less than 3.5 x 10-2 mol/liter,
This is not preferable in terms of preventing fogging.

In the present invention, the content of bromine ions in the color developer is preferably 1.0×10 −3 mol/liter or less. More preferably, it is 5×10 −4 mol/liter or less. If the bromide ion concentration is greater than 1.times.10@-3 mole/liter, development will be delayed and maximum density and sensitivity will be reduced.

The chlorine ions and bromine ions may be added directly to the developer, or may be eluted from the light-sensitive material into the developer during the development process. When added directly to color developers, sodium chloride,
Examples include potassium chloride, ammonium chloride, lithium chloride, nickel chloride, magnesium chloride, manganese chloride, calcium chloride, and cadmium chloride, among which preferred are sodium chloride and potassium chloride.

[0080] Alternatively, the brightening agent may be supplied from a fluorescent brightener added to the developer. Sodium bromide, potassium bromide, ammonium bromide,
Examples include lithium bromide, calcium bromide, magnesium bromide, manganese bromide, nickel bromide, cadmium bromide, cerium bromide, and thallium bromide, of which potassium bromide and sodium bromide are preferred.

[0081] When eluted from the photosensitive material during the development process,
Both chloride ions and bromine ions may be supplied from the emulsion, or may be supplied from a source other than the emulsion. The color developer used in the present invention preferably has a pH of 9 to 12, more preferably 9 to 11.0, and may contain other known developer component compounds. .

[0082] In order to maintain the above pH, it is preferable to use various buffers. Buffers include carbonate, phosphate, borate, tetraborate, hydroxybenzoate,
Glycyl salt, N,N-dimethylglycine salt, leucine salt, norleucine salt, guanine salt, 3,4-dihydroxyphenylalanine salt, alanine salt, aminobutyrate, 2-
amino-2-methyl-1,3-propanediol salt,
Valine salt, proline salt, trishydroxyaminomethane salt, lysine salt, etc. can be used. Especially carbonates,
Phosphate, tetraborate, and hydroxybenzoate have excellent solubility and buffering ability in the high pH range of pH 9.0 or higher,
It is particularly preferable to use these buffering agents because they have the advantage of not having any adverse effect on photographic performance (fogging, etc.) even when added to color developing solutions, and are inexpensive.

Specific examples of these buffers include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, and sodium borate. , potassium borate, sodium tetraborate (borax), potassium tetraborate, sodium o-hydroxybenzoate (
sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), 5-sulfo-2
-potassium hydroxybenzoate (potassium 5-sulfosalicylate), and the like. However, the present invention is not limited to these compounds.

[0084] The amount of the buffer added to the color developer is:
It is preferably 0.1 mol/liter or more, particularly preferably 0.1 mol/liter to 0.4 mol/liter.

[0085] In addition, various chelating agents can be used in the color developer as an anti-settling agent for calcium or magnesium or to improve the stability of the color developer. For example, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,N
',N'-tetramethylene sulfonic acid, transsilohexanediaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid , 1-hydroxyethylidene-1,1-diphosphonic acid, N,N'-bis(2-
Examples include hydroxybenzyl)ethylenediamine-N,N'-diacetic acid.

Two or more of these chelating agents may be used in combination, if necessary. These chelating agents may be added in an amount sufficient to sequester metal ions in the color developer. For example, it is about 0.1 g to 10 g per liter.

[0087] Any development accelerator can be added to the color developer if necessary. As a development accelerator,
-16088, 37-5987, 38-782
6, No. 44-12380, No. 45-9019, and U.S. Pat.
p-phenylenediamine compounds disclosed in No. 9829 and No. 50-15554, JP-A-50-137
No. 726, Japanese Patent Publication No. 1973-30074, Japanese Patent Publication No. 1987-1
Quaternary ammonium salts disclosed in No. 56826 and No. 52-43429, U.S. Patent No. 2,494,9
No. 03, No. 3,128,182, No. 4,230,
No. 796, No. 3,253,919, Special Publication No. 1977-
11431, U.S. Pat. No. 2,482,546, U.S. Pat. No. 2,596,926, U.S. Pat. No. 42-25201, U.S. Patent No. 3,128,183, Japanese Patent Publication No. 41-11431, No. 42-23883, and U.S. Patent No. 3,532,5
Polyalkylene oxides disclosed in publications such as No. 01 or specifications, 1-phenyl-3-pyrazolidones, imidazoles, etc. may be added as necessary.

In the present invention, any antifoggant can be added if necessary. As antifoggants, alkali metal halides such as sodium chloride, potassium bromide, potassium iodide, and organic antifoggants can be used. Examples of organic antifoggants include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2 Typical examples include nitrogen-containing heterocyclic compounds such as -thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, and adenine.

Color developers that can be applied to the present invention include:
Preferably, it contains an optical brightener. As the fluorescent brightener, 4,4'-diamino-2,2'-disulfostilbene compounds are preferred. The amount added is 0 to 5 g/liter, preferably 0.1 to 4 g/liter.

Further, various surfactants such as alkylsulfonic acids, arylsulfonic acids, aliphatic carboxylic acids, and aromatic carboxylic acids may be added as necessary. The processing temperature of the color developer applicable to the present invention is 30 to 50°C, preferably 35 to 50°C. The treatment time is 5 seconds to 30 seconds, preferably 5 seconds to 20 seconds, and more preferably 5 to 15 seconds. The smaller the amount of replenishment, the better, but 1 m2 of photosensitive material
Appropriately 20-600ml per bottle, preferably 30ml
~100ml.

The black and white developer contains known black and white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol. can be used alone or in combination.

[0092] The pH of these black and white developers is generally 9 to 9.
It is 12. The bleaching solution, bleach-fixing solution, and fixing solution that can be applied to the present invention will be explained below. As the bleaching agent used in the bleaching solution or bleach-fixing solution, any bleaching agent can be used, but especially organic complex salts of iron(III) (
For example, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, complex salts of aminopolyphosphonic acid, phosphonocarboxylic acid, and organic phosphonic acid) or organic acids such as citric acid, tartaric acid, and malic acid; persulfates; Hydrogen oxide and the like are preferred.

Among these, organic complex salts of iron (III) are particularly preferred from the viewpoint of rapid processing and prevention of environmental pollution. Aminopolycarboxylic acids, aminopolyphosphonic acids, or organic phosphonic acids or their salts useful for forming organic complex salts of iron(III) include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,3-
diaminopropanetetraacetic acid, propylenediaminetetraacetic acid,
Examples include nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, iminodiacetic acid, glycol ether diaminetetraacetic acid, and the like. These compounds may be sodium, potassium, thium or ammonium salts. Among these compounds, iron(III) complex salts of ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid, and methyliminodiacetic acid are preferred because of their high bleaching power. These ferric ion complex salts may be used in the form of complex salts, or ferric salts such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, and ferric phosphate. A ferric ion complex salt may be formed in a solution using a chelating agent such as aminopolycarboxylic acid, aminopolyphosphonic acid, or phosphonocarboxylic acid. Further, the chelating agent may be used in excess of the amount required to form the ferric ion complex. Among the iron complexes, aminopolycarboxylic acid iron complexes are preferred, and the amount added is 0.01
~1.0 mol/liter, preferably 0.05-0.5
0 mol/liter, more preferably 0.10 to 0.50
The amount is preferably 0.15 to 0.40 mol/liter, more preferably 0.15 to 0.40 mol/liter.

Various compounds can be used as bleach accelerators in the bleach solution, bleach-fix solution and/or their prebath. For example, US Patent No. 3,893,858, German Patent No. 1,290,812,
Compounds having a mercapto group or disulfide bond described in JP-A-53-95630, Research Disclosure No. 17129 (July 1978 issue), JP-A-45-8506, JP-A-52-20832
No. 53-32735, U.S. Patent No. 3,706,56
The thiourea compounds described in No. 1, etc., or halides such as iodine and bromide ions are preferred because they have excellent bleaching power.

Other bleaching solutions or bleach-fixing solutions that can be applied to the present invention include bromides (for example, potassium bromide, sodium bromide, ammonium bromide) or chlorides (for example, potassium chloride, sodium chloride, ammonium chloride). )
or a rehalogenating agent such as an iodide (eg, ammonium iodide). If desired, one or more inorganic acids having a pH buffering capacity such as borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, etc. Organic acids and their alkali metal or ammonium salts or corrosion inhibitors such as ammonium nitrate and guanidine can be added.

The fixing agent used in the bleach-fixing solution or the fixing solution is a known fixing agent, namely, a thiosulfate such as sodium thiosulfate or ammonium thiosulfate; a thiocyanate such as sodium thiocyanate or ammonium thiocyanate;
Ethylene bisthioglycolic acid, 3,6-dithia-1,
Water-soluble silver halide solubilizers such as thioether compounds such as 8-octanediol and thioureas,
These can be used alone or in combination of two or more. Further, a special bleach-fixing solution consisting of a combination of a fixing agent and a large amount of a halide such as potassium iodide as described in JP-A-55-155354 can also be used. In the present invention, the use of thiosulfates, particularly ammonium thiosulfates, is preferred. The amount of fixing agent per liter is preferably from 0.3 to 2 mol, more preferably from 0.5 to 1.0 mol.

p of the bleach-fix solution or fixer solution in the present invention
The H region is preferably 3 to 8, and particularly preferably 4 to 7. If the pH is lower than this, the desilvering performance is improved, but the deterioration of the solution and the leucoization of the cyan dye are accelerated. On the contrary, pH
If it is higher than this, desilvering will be delayed and stains will be more likely to occur.

The pH range of the bleaching solution in the present invention is 8 or less, preferably 2-7, particularly preferably 2-6. p
If H is lower than this, deterioration of the solution and leucoization of the cyan dye will be promoted, while if pH is higher than this, desilvering will be delayed and stains will easily occur.

In order to adjust the pH, hydrochloric acid, sulfuric acid, nitric acid, bicarbonate, ammonia, caustic potash, caustic soda, sodium carbonate, potassium carbonate, etc. can be added as necessary.

The bleach-fix solution may also contain various other fluorescent brighteners, antifoaming agents, surfactants, and organic solvents such as polyvinylpyrrolidone and methanol. Bleach-fix solutions and fixing solutions contain sulfites (e.g., sodium sulfite, potassium sulfite, ammonium sulfite, etc.), bisulfites (e.g., ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.), Metabisulfites (e.g. potassium metabisulfite,
Sodium metabisulfite, ammonium metabisulfite,
It is preferable to contain a sulfite ion releasing compound such as ). These compounds have approximately 0.0% in terms of sulfite ion.
The content is preferably from 0.2 to 1.0 mol/liter, more preferably from 0.04 to 0.6 mol/liter.

As a preservative, sulfite is generally added, but other substances such as ascorbic acid, carbonyl bisulfite adducts, or carbonyl compounds may also be added. Furthermore, buffering agents, optical brighteners, chelating agents, antifoaming agents, antifungal agents, etc. may be added as desired.

[0102] The bleach-fix solution of the present invention has a processing time of 5 seconds to 12 seconds.
0 seconds, preferably 10 seconds to 60 seconds. The processing temperature is 2
The temperature is 5°C to 60°C, preferably 30°C to 50°C. In addition, the replenishment amount is 20ml to 250ml per 1m2 of photosensitive material.
1, preferably 30 ml to 100 ml. Preservatives include sulfites (e.g. sodium sulfite, potassium sulfite, ammonium sulfite, etc.), bisulfites (e.g. ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.), metabisulfites (e.g. It is preferred to contain a sulfite ion releasing compound such as potassium bisulfite, sodium metabisulfite, ammonium metabisulfite, etc.). These compounds are preferably contained in an amount of about 0.02 to 1.0 mol/liter, more preferably 0.04 to 0.0 mol/liter in terms of sulfite ion.
6 mol/liter.

[0103] As a preservative, sulfites are generally added, but ascorbic acid, carbonyl bisulfite adducts, carbonyl compounds, etc. may also be added.

[0104] Furthermore, buffering agents, optical brighteners, chelating agents,
Antifoaming agents, antifungal agents, etc. may be added as desired. After desilvering treatment such as fixing or bleach-fixing, washing with water and/or stabilization treatment is generally performed.

The amount of washing water in the washing step can be set within a wide range depending on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the purpose, the washing water temperature, the number of washing tanks (number of stages), and various other conditions. Among these, the relationship between the number of flushing tanks and the amount of water in the multistage countercurrent method is described in the Journal of the
Society of Motion Picture and
Television Engineers (Journal o
f the Society of Motion P
ictureand Television Engi
neers) Volume 64, p. 248 ~ 253 (19
This can be obtained using the method described in the May 1955 issue). Normally, the number of stages in the multistage countercurrent system is preferably 2 to 6.
Particularly preferably 2 to 5.

[0106] According to the multistage countercurrent method, the amount of washing water can be greatly reduced, for example, to 500 ml or less per 1 m2 of photosensitive material, and the effect of the present invention is remarkable. As the time increases, problems arise such as bacteria propagating and resulting floating matter adhering to the photosensitive material. As a solution to this problem, Japanese Patent Application Laid-open No. 62-
The method for reducing calcium and magnesium described in Japanese Patent No. 288838 can be used very effectively. In addition, isothiazolone compounds and thiabendazoles described in JP-A No. 57-8542, JP-A No. 61-120
Chlorine-based disinfectants such as chlorinated sodium isocyanurate described in Publication No. 145, benzotriazole and copper ions described in JP-A-61-267761, and others such as "Chemistry of Antibacterial and Antifungal" by Hiroshi Horiguchi (1986) Sankyo Publishing, edited by Hygiene Technology Association, "Microbial sterilization, sterilization, and anti-mold technology" (1982)
It is also possible to use the fungicides described in "Encyclopedia of Antibacterial and Antifungal Agents" (1986), edited by the Society of Industrial Science and Technology and the Japan Society of Antibacterial and Mildew Prevention.

Furthermore, in the washing water, a surfactant as a draining agent and a chelating agent typified by EDTA as a water softener can be used. Continue with the above washing process or
Alternatively, it is also possible to directly treat with a stabilizing solution without going through a water washing step. A compound having an image stabilizing function is added to the stabilizing solution, such as an aldehyde compound typified by formalin, a buffer for adjusting the membrane pH suitable for dye stabilization, and an ammonium compound. Further, in order to prevent the proliferation of bacteria in the liquid and to impart anti-mold properties to the photographic material after processing, the various disinfectants and anti-mold agents described above can be used.

[0108] Furthermore, surfactants, optical brighteners, and hardeners can also be added. In the processing of the photosensitive material of the present invention, when stabilization is performed directly without going through a water washing step,
JP-A-57-8543, JP-A No. 58-14834, JP-A No. 6
All known methods described in JP 0-220345 and the like can be used.

Others: 1-hydroxyethylidene-1,
It is also a preferred embodiment to use a chelating agent such as 1-diphosphonic acid or ethylenediaminetemethylenephosphonic acid, or a magnesium or bismuth compound.

A so-called rinsing solution can also be used as a washing solution or a stabilizing solution after the desilvering treatment. The preferred pH of the water washing step or stabilization step is 4 to 10, more preferably 5 to 8. Although the temperature can be set variously depending on the use and characteristics of the photosensitive material, it is generally 20°C to 50°C, preferably 25°C to 45°C. Although the time can be set arbitrarily, a shorter time is preferable from the viewpoint of reducing processing time. Preferably it is 10 seconds to 60 seconds, more preferably 15 seconds to 45 seconds. The smaller the amount of replenishment, the better from the viewpoints of running costs, reduced emissions, ease of handling, and the like.

A specific preferred amount of replenishment is 0.5 to 50 times, preferably 3 to 40 times, the amount brought in from the prebath per unit area of the photosensitive material. or 1m2 of photosensitive material
500 ml or less, preferably 300 ml or less. Further, replenishment may be performed continuously or intermittently.

[0112] The liquid used in the water washing and/or stabilization step was
Furthermore, it can also be used in a pre-process. An example of this is the use of a multi-stage countercurrent method to reduce overflow of washing water.
The amount of waste liquid can be reduced by flowing the concentrated liquid into the bleach-fixing bath, which is a pre-bath, and replenishing the bleach-fixing bath with concentrated liquid.

One embodiment of the present invention will be described with reference to FIG. 1 attached. However, the present invention is not limited to this embodiment, and all modifications are possible based on the technical idea of the present invention.

FIG. 1 shows a silver salt photographic color paper processing apparatus to which the present invention is applied. This processing apparatus forms an image on color paper by developing, bleach-fixing, washing (rinsing) color paper that has been exposed to light based on a positive original, and then drying the paper. Color paper (hereinafter referred to as photosensitive material) processed by this processing apparatus is color-developed with a color developer containing an aromatic primary amine color developing agent.

[0115] Inside the processing device, there are a developing tank 2, a bleach-fixing tank 3,
A washing tank 4, a draining section 7, and a drying section 11 are successively provided, and the exposed photosensitive material S is developed, bleach-fixed, washed, and then dried before being carried out from the processing apparatus. The developing tank 2, bleach-fixing tank 3, washing tank 4, draining section 7, and drying section 11 are provided with conveying rollers 51 that transport the photosensitive material along the path shown in the figure, and the photosensitive material S is placed horizontally as an emulsion. It is transported with the surface facing upward. Further, the draining section 7 has the function of supporting the photographic material with airflow and simultaneously removing water droplets.

The bleach-fix tank 3 shown in FIG. 1 is preferably composed of a plurality of tanks (two tanks (3a and 3b) in FIG. 1). There may be a bleach-fixing process consisting of three or more tanks. ] When the photosensitive material being processed is transferred from the inlet of the first tank of the bleach-fix tank 3 to the final tank, it is transferred while being immersed in the processing solution. At this time, a blade (or shutter) is provided at the entrance and exit between each tank of the bleach-fix tank 3.

[0117] In a preferred embodiment, the length of the process path from the inlet of the first tank of the bleach-fix tank 3 to the final tank does not change regardless of the number of tanks. The washing tank 4 preferably consists of a plurality of tanks, and in this embodiment, the washing tank 4 is provided with five layers 4a to 4e. Each of the washing tanks 4a to 4e is arranged in cascade piping, and the cleanliness of the washing water gradually decreases from the last tank 4e to the first tank 4a. The developer tank 2, bleach-fix tank 3, and washing tank 4 are refilled with replenisher according to the amount of photosensitive material S processed, and in the bleach-fix tank 3, the bleach-fix replenisher is added to the final stage tank 3b. However, in the washing tank 4, the final stage tank 4e is replenished with fresh washing water.

The photosensitive material is conveyed while being held between a conveyance roller 51 and a backup roller 52, and a conveyance guide 53 is placed in the middle of the conveyance, and another kind of conveyance guide 5 is placed at the bottom of the tank.
4 is installed.

Conveyance in the drying section 11 is carried out by a draining roll 56 and a drying section conveyance roll 57. Drying is performed by hot air passed through slits 111 from a hot air blower 110.

FIG. 2 is a diagram showing a developing processing apparatus for photographic light-sensitive materials used in a comparative example of the present invention. It is a conventional processing apparatus, and unlike the processing apparatus shown in FIG. 1, the bleach-fixing tank is composed of one tank. The path length of the treatment process is the same as the total path length of the multiple tanks shown in FIG. In addition, other parts are shown in Figure 1.
It has the same configuration as .

[0121]

【Example】

Example 1 Preparation of Sample 1 After corona discharge treatment was applied to the surface of a paper support laminated on both sides with polyethylene, a gelatin undercoat layer containing sodium dodecylbenzene sulfonate was applied, and various photographic constituent layers were further applied. A multilayer color photographic paper (sample 1) having the layer structure shown in FIG. The coating solution was prepared as follows.

Fifth layer coating solution preparation Cyan coupler (Exc) 32.0g, color image stabilizer (Cpd-2) 3.0g, color image stabilizer (Cpd-4)
2.0g, color image stabilizer (Cpd-6) 18.0g
, 40.0 g of color image stabilizer (Cpd-7) and 5.0 g of color image stabilizer (Cpd-8), and 50.0 g of ethyl acetate.
0 cc and 14.0 g of solvent (Solv-6) were added and dissolved, and this solution was added to 500 cc of a 20% gelatin aqueous solution containing 8 cc of sodium dodecylbenzenesulfonate, and then emulsified and dispersed using an ultrasonic homogenizer to obtain an emulsified dispersion. Prepared. On the other hand, silver chlorobromide emulsion (cubic,
A large emulsion with an average grain size of 0.58 μm and a grain size of 0.4 μm.
1:4 mixture (Ag molar ratio) with 5μm small size emulsion
. The coefficient of variation of the grain size distribution was 0.09 and 0.11, and emulsions of each size contained 0.6 mol % of silver bromide locally on a part of the grain surface). In this emulsion, the following red-sensitive sensitizing dye E was contained per mole of silver at 0.9 x 10-4 mol for large-sized emulsions and 1.1 x 10-4 for small-sized emulsions. 4 moles were added. Further, chemical ripening of this emulsion was carried out by adding a sulfur sensitizer and a gold sensitizer. The above emulsified dispersion and this red-sensitive silver chlorobromide emulsion were mixed and dissolved to prepare a fifth layer coating solution having the composition shown below.

Coating solutions for the first to fourth, sixth and seventh layers were also prepared in the same manner as the fifth layer coating solution. As the gelatin hardening agent for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used.

[0124] In addition, Cpd-10 and Cpd-11 were added to each layer.
The total amount is 25.0mg/m2 and 50.0mg respectively.
/m2. The following spectral sensitizing dyes were used in the silver chlorobromide emulsion of each light-sensitive emulsion layer.

That is, in the blue-sensitive emulsion layer, sensitizing dye A and sensitizing dye B were added per mole of silver halide, 2.0 x 10-4 mole each for large-sized emulsions, and 2.0 x 10-4 moles each for small-sized emulsions. 2.5 x 10-4 mol each,

0126
]

[Formula 1] In the green-sensitive emulsion layer, sensitizing dye C is added per mol of silver halide, 4.0 x 10 -4 mol for large emulsions and 5.6 x 10 mol for small emulsions. -4 mol and sensitizing dye D per mol of silver halide, 7.0 x 10-5 mol for large size emulsions, 1.0 x 10-5 mol for small size emulsions,

[0127]

[Formula 2] In the red-sensitive emulsion layer, sensitizing dye E is added per mol of silver halide, 0.9 x 10-4 mol for large emulsions and 1.1 x 10 mol for small emulsions. -4 mol each were added.

[0128]

[Chemical Formula 3] Furthermore, the following compound H was added at 2.0% per mole of silver halide.
6 x 10-3 moles were added.

[0129]

[Chemical formula 4] In addition, 1-(5-methylureidophenyl)-5-mercaptotetrazole was added per mole of silver halide to the blue-sensitive emulsion layer, green-sensitive emulsion layer, and red-sensitive emulsion layer, respectively.
8.5 x 10-5 mol, 7.7 x 10-4 mol, 2
．． 5×10 −4 mol was added.

Further, for the blue-sensitive emulsion layer and the green-sensitive emulsion layer, 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene was added per mole of silver halide, respectively.
1 x 10-4 mol and 2 x 10-4 mol were added. In addition, the following dyes (coating amounts are shown in parentheses) were added to the emulsion layer to prevent irradiation.

[0131]

embedded image (Layer structure) The composition of each layer is shown below. The number is the coating amount (g
/m2). The silver halide emulsion represents the coated amount in terms of silver.

Support polyethylene laminate paper [white pigment (TiO2) in the polyethylene on the first layer side
First layer (blue-sensitive emulsion layer) Silver chlorobromide emulsion (cubic, 3:7 of a large emulsion with an average grain size of 0.88 μm and a small emulsion with an average grain size of 0.70 μm)
Mixture (silver molar ratio). The coefficient of variation of grain size distribution is 0.88 and 0.10, respectively, and silver bromide is 0.88 and 0.10 for each size emulsion.
3 mol% was locally contained in a part of the particle surface) 0
．． 30 gelatin
1.86 yellow coupler (E
xY) 0.82 color image stabilizer (Cpd-1)
0.19 solvent (Solv-3)
0.18 solvent (Solv-7)
0.18 color image stabilizer (Cpd-7)
0.06 Second layer (color mixing prevention layer) Gelatin
0.99 color mixing inhibitor (Cpd-5)
0.08 solvent (Solv-1)
0.16 solvent (Solv-4)
0.0
8 Third layer (green-sensitive emulsion layer) Silver chlorobromide emulsion (cubic, consisting of a large emulsion with an average grain size of 0.55 μm and a small emulsion with an average grain size of 0.39 μm)
3 mixture (silver molar ratio). The coefficient of variation of grain size distribution is 0.10 and 0.08, respectively, and each size emulsion is AgBr.
(0.8 mol% was locally contained in a part of the particle surface)
0.12 gelatin
1.2
4 magenta coupler (ExM)
0.23 color image stabilizer (Cpd-2)
0.03 color image stabilizer (Cpd-3)
0.16 color image stabilizer (Cpd-4)
0.02 color image stabilizer (Cp
d-9) 0
．． 02 solvent (Solv-2)
0.40 Fourth layer (ultraviolet absorption layer) Gelatin
1.58 Ultraviolet absorber (UV-1)
0.47 Color mixing prevention agent (Cpd-5)
0.05 solvent (Solv-5)
0.24 Fifth layer (red-sensitive emulsion layer) Silver chlorobromide emulsion (cubic, consisting of a large emulsion with an average grain size of 0.58 μm and a small emulsion with an average grain size of 0.45 μm):
4 mixture (silver molar ratio). The coefficient of variation of particle size distribution is 0
．． 09 and 0.11, AgBr 0.6 for each size emulsion
mol% was locally contained in a part of the particle surface) 0.2
3 Gelatin
1.34 cyan coupler (ExC)
0.32 color image stabilizer (Cpd-2)
0.03 color image stabilizer (Cpd-4)
0.02 color image stabilizer (C
pd-6)
0.18 color image stabilizer (Cpd-7)
0.40 color image stabilizer (Cpd-
8) 0.0
5 Solvent (Solv-6)
0.14 Sixth layer (ultraviolet absorption layer) Gelatin
0.53 Ultraviolet absorber (UV-1)
0.16 color mixing inhibitor (Cpd-5)
0.02 solvent (Solv-5)
0.08 Seventh layer (protective layer) Gelatin
1.33 Acrylic modified copolymer of polyvinyl alcohol (degree of modification 17%) 0.
17 Liquid paraffin
0.03

[0133]

[C6]

[0134]

[C7]

[0135]

[Chemical formula 8]

[0136]

[Chemical formula 9]

[0137]

[Chemical formula 10]

[0138]

[Chemical formula 11]

[0139]

[Chemical formula 12]

[0140]

Preparation of Sample 2 Sample 2 was prepared by changing the amount of gelatin in Sample 1 of the present invention as described below.

[0141] 1st layer gelatin 0.69
g/m2 2nd layer gelatin 0.74 g
/m2 3rd layer gelatin 0.82 g/
m2 4th layer Gelatin 0.61 g/m
2 5th layer Gelatin 0.89 g/m2
6th layer gelatin 0.40 g/m2
7th layer Gelatin 0.62 g/m2 The above-mentioned samples 1 and 2 of the present invention were used as light-sensitive materials.

Samples 1 and 2 were subjected to gradation exposure using a three-color separation filter for sensitometry using a sensitometer (FW model manufactured by Fuji Photo Film Co., Ltd., color temperature of light source: 3200°K). The exposure at this time was 2 with an exposure time of 0.1 seconds.
This was done so that the exposure amount was 50 CMS.

The exposed sample was developed using the processing apparatus shown in FIG. 1 according to the specifications of the present invention. Further, as a comparative example, development processing was performed using the processing apparatus shown in FIG. Processing process Temperature Time Replenisher* Tank capacity Color development
39℃ 20 seconds 80ml 10.
0 liter bleach fixing 40℃
20 seconds 60ml 5.0 liters
2 Rinse ■ 41℃ 7
seconds - 2.0 liters
Rinse ■ 41℃ 7 seconds -
2.0 liter rinse■
41℃ 7 seconds - 2
．． 0 liter rinse■ 41℃
7 seconds - 2.0 liters
Rinse ■ 41℃ 7 seconds
100ml 2.0 liters Drying 70-80℃ 15 seconds
*The amount of replenishment is expressed as the amount per 1 m2 of photosensitive material.

[0144] In addition, a 5-tank counter-current system was used for rinsing (①→②). In FIG. 2, the same apparatus as in FIG. 1 was used except that the bleach-fix tank was changed to 10.0 liters. The composition of each treatment liquid is as follows. bleach-fix solution
Tank fluid Replenishment fluid Water
400ml
400 ml ammonium thiosulfate (
70%) 100 ml 250
ml sodium sulfite
40g 100
g Iron(III) ethylenediaminetetraacetate

Ammonium dihydrate salt
73 g 183 g Ethylenediaminetetraacetic acid
3.4 g 8.5 g Ammonium bromide
20 g 50 g Nitric acid (67%
)
9.6 g 24 g Add water
1000ml 1000ml
pH (25℃)
5.80 5.
10 Rinse solution (tank solution and refill solution are the same) Ion exchange water (calcium, magnesium 3pp each
m or less) As a comparative example, the sample was processed using the processing apparatus shown in FIG.

[0145] Further, continuous treatment was carried out until the capacity of the tank became twice as large. Table 6 shows the stains when the samples before and after continuous treatment were left at 80° C. and relative humidity 70% RH for 10 days.

Table 6 4
Spectral absorption value at 50 nm (reflection measurement) Item
Equipment Sensitive material Before continuous processing
After continuous processing Present invention 1 Apparatus diagram 1 1 0
．． 14 0.18 Comparative Example 1 Device Diagram 2 1 0.19
0.44 Present invention 2
Equipment diagram 1 2 0.12
0.16
Comparative example 2 Device diagram 2 2
0.17 0.40
From the results shown in Table 6, it can be seen that the effect of the treatment by the apparatus of the present invention is large.

(Example 2) Sample 2 of the photosensitive material was processed using the apparatus shown in FIGS. 1 and 2, and the processing time was changed to 20 seconds, 27 seconds, and 45 seconds (20 seconds) by changing the depth of the bleach-fix tank.
The second processing was set to the same as the processing in Example 1 above for testing. The times for the development process and the water washing process are the same as in Example 1.

Table 7 shows the results of tests conducted under the same storage conditions as in Example 1 for the finished prints. Table 7 Item Bleach-fixing time Equipment
Before continuous processing After continuous processing
Present invention 2 20 seconds
Figure 1 0.12 0.16 Comparative example 2 20 seconds Figure 2
0.17 0.40
Present invention 3 27 seconds
Figure 1 0.11 0.14
Comparative example 3 27 seconds
Figure 2 0.14 0.
28 Comparative example 4 4
5 seconds Figure 1 0.12
0.16 Comparative example 5
45 seconds Figure 2 0.
13 0.17 From the results shown in Table 7, it can be seen that when the bleach-fixing time is 20 seconds or 27 seconds, the effect of the treatment by the apparatus of the present invention is large. Also, a bleach-fix time of 45 seconds improves staining on white backgrounds, but does not achieve rapid processing, which is the first objective of the present invention.

(Example 3) Example 2 except that the amount or type of developing agent in the color developer used in Example 2 was changed as shown in Table 8 below.
Processed using a color developer with the same composition as used in
The effect of treatment by the apparatus of the present invention was investigated.

Table 8 Name of developing agent
Usage amount (g/liter)
Tank liquid Replenishment liquid Invention 4 N-ethyl-
N-(3-hydroxy 6.4
12.6 Cypropyl)-3-methyl-4
-Aminoaniline dipalator
Ensulfonate
Present invention 5 4-
Amino-N-ethyl-N-β
-Methanesulfonamidoethyl 10.1
15.2 Ru-3-methylaniline
Present invention 6
Same as above
5.1 11.5 Invention 7 4-amino-N-ethyl-N-
β-hydroxyethyl-3-methane

Chillaniline
6.8 10.2
Present invention 8 Same as above
4.3
6.6 The bleach-fixing time was 20 seconds.

[0151] Inventions 4 to 8, including Invention 1, can also achieve a temperature of 80° C. and a relative humidity of 7 by using two bleach-fixing tanks.
An effect was observed in improving the staining of the white background after 7 days under 0% RH, and the effect was particularly large in the samples of Inventions 1, 5, and 7 containing a large amount of developing agent.

[0152]

Effects of the Invention According to the present invention, there are two or more processing tanks for processing processes such as bleaching in a developing processing apparatus, and the amount of residual developing agent at the time when the processing in the first processing tank is completed. By controlling the amount of residual developing agent so that it is at least 1.5 times the amount of residual developing agent at the end of processing in the final processing tank of the processing tank, it is possible to reduce the The stain that occurs in the non-image areas of the image when the finished photographic material is subjected to wet heat treatment due to insufficient removal of the developing agent has been eliminated.

In particular, in the rapid development of color photographic materials, by using two or more processing tanks for processes such as bleaching, even when the processing time for processes such as bleaching is reduced to 30 seconds or less, the finished photographic material can be improved. No stains occur in non-image areas of the image.

[Brief explanation of drawings]

FIG. 1 is a schematic diagram of a silver halide photographic material processing apparatus which is an embodiment of the present invention.

FIG. 2 is a schematic diagram of a conventional silver halide photographic material processing apparatus.

[Explanation of symbols]

2 Developing tank 3 Bleach-fix tank 4 Washing tank 7 Draining section 11 Drying section 51 Conveyance roller 52 Backup roller 53 Conveyance guide 54 Conveyance guide 56 Draining roller 57 Drying section conveyance roller 110 Hot air blower 111 Drying section slit S Photosensitive material

Claims (6)

[Claims] Claim 1. A method for processing a silver halide photographic light-sensitive material, comprising at least one step each containing a developing agent and having a developing function, and at least one step having a bleaching function and/or a fixing function, wherein the bleaching function and/or The process having the fixing function consists of at least two tanks having substantially the same function, and the amount of the developing agent contained in the silver halide photographic light-sensitive material that has completed the first tank of the process having the same function has the same function. A processing method in which the amount of developing agent is controlled to be 1.5 times or more the amount of developing agent contained in the silver halide photographic light-sensitive material that has completed the final bath. 2. A method for processing a silver halide photographic material, comprising at least one step each containing a developing agent and having a developing function, and at least one step having a bleaching function and/or a fixing function, wherein the bleaching function and/or The process having the fixing function consists of at least two tanks having substantially the same function, and the processing time of the process having the same function is 3.
A processing method controlled to be within 0 seconds. 3. In the process of the processing method according to claim 1 or 2, which comprises at least two tanks and has a bleaching function and/or a fixing function, the silver halide photographic light-sensitive material in the process comprises: 1. A method for processing a silver halide photographic material, which comprises transferring the material while being immersed in a processing solution. 4. A processing apparatus for a silver halide photographic light-sensitive material having at least one process containing a developing agent and having a developing function and at least one process having a bleaching function and/or a fixing function. The process having the same function consists of at least two successive tanks having substantially the same function and is equipped with a replenisher supply means, and the developing process contains the photosensitive material that has completed the first tank of the process having the same function. A processing device in which the amount of the main agent is controlled to be 1.5 times or more the amount of the developing agent contained in the photosensitive material that has completed the final bath having the same function. 5. A processing apparatus for silver halide photographic light-sensitive materials having at least one process containing a developing agent and having a developing function and at least one process having a bleaching function and/or a fixing function, A processing apparatus comprising at least two consecutive tanks having substantially the same function, and comprising a replenisher supply means, and controlled so that the processing time of the processing step is within 30 seconds. 6. In the processing apparatus according to claim 4 or 5, in which the process comprises at least two consecutive tanks and has a bleaching function and/or a fixing function, silver halide photographic exposure in the process 1. A processing apparatus for silver halide photographic light-sensitive materials, characterized in that the material is transferred while being immersed in a processing solution.