JPH06161084A - Automatic developing machine for silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide the automatic developing machine for silver halide photographic sensitive materials which processes the silver halide photographic sensitive materials and more specifically the automatic developing machine for the silver halide photographic sensitive materials with which the machine is made compact, dissolving operation is eliminated, workability is greatly improved and chemical stability is greatly improved. CONSTITUTION:The solid processing agents contg. plural components for this automatic developing machine for the silver halide photographic sensitive materials are the solid processing agents 13 which are previously divided and weighted to a replenishing unit or the integrated solid processing agents which are in a specified unit and are uniform in the entire component and is stored a processing tank 1. The automatic developing machine has a means 17 which charges these solid processing agents 13 from above to below into the processing tank by utilizing gravity and a replenishing water supplying means 42 which supplies water to the processing tank 1. The charging quantity per time of the solid processing agents 13 is in a 0.5 to 30g range. A replenishing water supply control means for controlling the supply of the replenishing water of the replenishing water supplying means 42 in such a manner that the replenishing water is supplied uniformly in compliance with the processing quantity of the silver halide photographic sensitive materials is provided.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an automatic developing machine for silver halide photographic light-sensitive materials (hereinafter, simply referred to as an automatic developing machine) for processing a silver halide photographic light-sensitive material (hereinafter also referred to as a light-sensitive material or a photographic material). Or, it may also be an automatic processing machine), more specifically for silver halide photographic light-sensitive materials, in which compactness and dissolution work are eliminated, workability is greatly improved, and chemical stability is dramatically improved. It relates to an automatic processor.

[0002]

2. Description of the Related Art A silver halide color photographic light-sensitive material is processed by processes such as development, desilvering, washing and stabilization after exposure. The black-and-white silver halide photographic light-sensitive material is developed and fixed after exposure. Black-and-white developer, color developer, bleaching solution for desilvering process, bleach-fixing solution, fixing solution for fixing process, tap water or ion-exchanged water for washing, stabilizing solution for anhydrous washing, and dye stabilization Stabilizers are used for each treatment. A liquid having a processing function for performing each of these processing steps is called a processing liquid. The temperature of each processing solution is usually adjusted to 30 to 40 ° C., and the light-sensitive material is dipped in these processing solutions for processing.

Such processing is usually carried out by sequentially conveying the inside of a processing tank containing the above-mentioned processing liquid by an automatic developing machine (hereinafter referred to as an automatic processor) or the like. Here, the automatic developing machine has a developing section, a fixing section, a desilvering section, a washing or stabilizing section and a drying section, and has means for automatically and sequentially transporting the photographic light-sensitive material in each processing tank section. Generally refers to a developing machine.

In the case of processing with such an automatic processor, a method of replenishing a processing agent is generally widely used in order to keep the activity of the processing solution in the processing tank constant. As the treatment agent replenishing method, a means for preparing a replenisher solution in which the treatment agent is dissolved is widely used. Specifically, the processing operation is performed while the preliminarily prepared replenishing solution is supplied from the replenishing tank into the processing tank at appropriate times.

In this case, the replenishing liquid itself stored in the replenishing tank is generally prepared and prepared in another place, but in a minilab or the like, a fixed amount is stored in the replenishing tank installed close to the developing machine. It is usually adjusted all at once, but in its production, dissolution by hand or dissolution and mixing by a mixer has been performed. That is, the processing agents for silver halide photographic light-sensitive materials (hereinafter sometimes referred to as photographic processing agents) are commercially available in powder or liquid form. The solution is prepared by dissolving it in, and even when it is in a liquid state, it is concentrated, so a certain amount of water is added and the mixture is simply stirred and diluted before use.

The refill tank may be installed beside the automatic machine, and it is necessary to secure a considerable space. Also,
Even in the minilab, which has been increasing rapidly in recent years, the refill tank is built into the machine itself, but at least 5 liters ~
It is necessary for each 10 liters of liquid, and it is necessary to secure the space for this replenishment tank. Replenishing processing agents are divided into several parts to obtain good and stable performance during photographic processing. The color developing solution for color is divided into 3 to 4 parts, and the replenisher for the bleach-fixing solution for color is divided into a ferric salt of organic acid which is an oxidizing agent and a thiosulfuric acid part which is a reducing agent. When the replenisher is prepared, the concentrated part of the ferric organic acid salt and the concentrated part containing thiosulfate are mixed and a certain amount of water is added for use.

The concentrated parts are put in a container such as a plastic container, and these are put together in an outer bag (for example, a cardboard box) and sold as a unit.

The replenishing treatment agent in which the above-mentioned part agent is made into a kit is used after dissolving, diluting, mixing and finishing to a fixed amount, but the replenishing treatment agent has the following drawbacks. First, most of the conventional kits are concentrated and concentrated aqueous solutions to improve workability, and most of them have pH of 2.0 or less or
It is an extremely dangerous aqueous solution of 12.0 or more, and it is often dangerous to the human body such as adhesion to the skin, and it is often a strong oxidizing agent or reducing agent, which is extremely dangerous corrosive for transportation by ship or aircraft. have. Further, since it is an aqueous solution, its solubility is limited, and its weight and volume are larger than those of a solid. As mentioned above, since the concentrate is a dangerous substance, it is necessary that the container does not break even if dropped from a certain height and the liquid does not spill. Is a problem.

Secondly, each part agent is placed in a container,
Depending on the replenishment processing agent, the number of part agents is several, and the number of containers is considerably large when it becomes one unit, which requires a lot of space for storage and transportation. For example, the color developing replenisher for CPK-2-20QA, which is a processing solution for color paper, is 10
The preservative-containing kit is divided into Part A, the color-developing agent-containing kit is divided into Part B, and the alkaline agent is divided into Part C with 1 as 1 unit, and each of A, B and C is contained in a 500 ml poly container. Similarly, the bleach-fixing solution has 8 l as a unit, and the parting agent is divided into 3 bottles, and the stabilizing solution has 10 l as a unit, and the parting agent is divided into 2 bottles. Each of these replenishers will be stored and transported in outer boxes of various sizes, but a stabilizing solution with a small outer box measures about 17 cm x 14 cm.
It is a relatively large bleach-fixing agent with a size of 16.5 cm x 18.5 cm x 30.5 cm
It becomes × 22.5cm, and it can be stacked only with the same kind of replenisher on storage, transportation or in a store, and eventually it requires a lot of space.

The third drawback is the disposal of empty containers. In recent years, there has been a strong demand for environmental conservation and resource saving mainly in Europe and the United States, and the disposal of plastic containers has become a problem especially in the photographic field. Although the plastic container for photography is cheap and convenient for storage and transportation and has excellent chemical resistance, the plastic container has little biodegradability,
When accumulated and incinerated, a large amount of carbon dioxide gas is generated, which is one of the causes of global warming and acid rain. Also, as a user's problem, a large number of plastic containers are piled up in a narrow work space. However, it has been pointed out that it cannot be crushed due to its strength, and the space is narrowed.

Fourth, the chemical is very unstable. The life of the replenisher is usually 2 weeks even with the floating lid. In recent years, however, the replenishment amount of each processing solution has been lowered, and 10 liters of the replenishing solution is often used for more than one month in a minilab that receives an average of 30 color films per day. In such a case, the replenisher in the replenishment tank is much more exposed to air than the replenisher in the replenishment tank and deteriorates. Therefore, it often happens that replenishment has no meaning at all. . Therefore, the device for reducing the refill tank to 5 l and the device for accommodating the refill kit as small as 5 l have been devised. In this case, there is a drawback that a packaging material is further required.

Another example is a color developing replenisher for color paper. When a color developing replenisher for color paper is prepared, a certain amount of water is put in a replenishing tank and then a preservative-containing concentrate kit A is prepared. Then, the color developing agent-containing concentration kit B is added and stirred, and then the alkali agent-containing concentration kit C is added and stirred, and finally water is added to complete a certain amount. At that time, some problems are likely to occur. For example, if the stirring is insufficient or if the first water is forgotten to be added, crystals of the color developing agent tend to precipitate, which accumulates in the bellows pump and is not replenished, resulting in unstable photographic performance. Or the bellows pump may be damaged. Further, the concentration kit may not be used immediately after the production, but may be used one year after the production, and in some cases, the color developing agent or preservative may be oxidized and the performance may become unstable.

It is known that color development replenishers made from concentrated kits and dusts also have some problems in replenishment tanks. For example, if the replenisher is not used for a long period of time, crystals may adhere to the wall of the refill tank,
In addition, the replenisher may be easily oxidized and tar may be generated. In addition, depending on the storage conditions, there is a problem that components that easily crystallize in the replenisher, such as color developing agents, will precipitate at low temperatures.Therefore, depending on the manufacturer, the storage conditions of the replenisher may be specified and managed by the user. It is the actual situation that I am instructing.

As described above, the means for preparing a replenishing solution using a commonly used concentration kit or the means for preparing a replenishing solution using a powder is exemplified by a color developing solution for color paper. There are the above-mentioned problems, and similar problems occur with bleach-fixing solutions, bleaching solutions and fixing solutions. For example, the bleach-fixing solution has a characteristic that storage stability is extremely poor. Because the bleach-fixing process is a process immediately after a color developing solution having a high pH, and since this alkaline color-fixing solution is usually brought in by the paper to be processed, the acidity is high and the pH is extremely low for the purpose of neutralization. Is customary. At a low pH, it is said that a bleach-fix solution composed of thiosulfate and an oxidizer has a markedly poor storability and a replenisher is prepared to make low replenishment impossible. In addition to this, the same applies to the fixing solution and the stabilizing solution.

Another problem is that the replenisher is only being concentrated as the replenisher is being made lower and faster, and the recent replenisher is usually concentrated to the limit of solubility. This means that the storability of the replenisher only deteriorates, and there are many practical problems such as crystal precipitation.

On the other hand, a means for directly replenishing the concentration kit is known, in addition to the means for preparing a replenishing solution using the concentration kit or powder as described above. In this means, in order to improve the inefficiency of the dissolution work, the concentration kit is directly replenished to the treatment tank by using a supplying means such as a bellows pump, and a certain amount of replenishing water is independently supplied. Certainly, compared to the above-mentioned means for adjusting the replenisher solution from the concentration kit or powder, this means does not require a liquid preparation operation. Alternatively, since a replenisher is not prepared, the problem of storability is eliminated.

However, the above-mentioned means also have many problems. That is, in order to supply the concentration kit, a tank for the concentration kit and a pump as a supply means are newly required, which is a problem that the automatic developing machine becomes large. For example, taking CPK-2-20 which is a processing solution for color paper as an example, there are 3 parts of a color development replenisher replenisher concentration kit, a bleach-fix replenisher replenisher concentration kit 3 parts, and a stable replenisher concentration The kit is in 2 parts, and when it is supplied, there are 8 tanks for the concentration kit and 8 pumps.
I need a stand. In the case of the conventional replenishment system, it is sufficient to have a tank and a pump for each replenisher, so that three replenishers are sufficient. Looking only at the case of supplying the concentration kit like this, more tanks and pumps are required than the conventional means,
Furthermore, a pump for adjusted water is also required. Further, the accuracy of the bellows pump is not so high, and it is difficult to simultaneously discharge a plurality of liquids with high accuracy, and there is a drawback that the components are crumpled.

Further, since the concentration kit is a concentrated liquid, crystals are likely to precipitate near the outlet of the replenishing nozzle, which makes maintenance difficult. Further, there is a problem that the bellows pump does not have such a high supply accuracy, and when replenishing the concentrated liquid, the replenishment accuracy is likely to be significantly different, resulting in a large variation in photographic performance. As another problem, the conventional replenishment method and the amount of waste poly container do not change even if the waste poly container is used as a means for supplying the concentration kit.

There have been some proposals for eliminating the plastic container and improving the chemical stability of the replenisher by means other than the above. For example, JP-A-58-11032 discloses a technique of encapsulating a developing component in microcapsules, and JP-A-51-61837 discloses a photographic tablet containing a disintegrant. Furthermore, JP-A Nos. 2-109042 and 2-109043
Nos. 3,397,35 and 3,397,39 disclose means for using a granulated photographic processing agent having a certain average particle size. The photographic tablet containing the disintegrating agent described in JP-A-51-61837 merely proposes a tablet that can be easily dissolved in water. Thoughts cannot be recalled at all. Further, JP-A-2-19042 describes a granulated photographic processing agent having a certain average particle size.

[0020] However, the above-mentioned publication proposes a compact automatic developing machine in the automatic processor, which eliminates the work of dissolving the replenisher to sufficiently simplify workability and obtain stable photographic performance, and eliminates the replenishment tank. is not. on the other hand,
As means for eliminating the need for a prior melting operation, JP-A-3-
No. 11344 discloses a technique in which a paste-like part agent is extruded in an amount corresponding to the mixing ratio of the part agent from each unit container, and the extruded part agent is diluted to a predetermined concentration with precision and supplied. Although this method certainly reduces the dissolution work or almost eliminates the dissolution work, the paste-like part agent lacks stability and can be extruded in a certain amount over a long period of time because it contains a solvent. If it is difficult and the frequency of use is low, the nozzle will be easily clogged,
It is difficult to keep the photographic performance constant. Further, a container for containing the paste is required, and in this case, a flexible and hard-to-break material is required, and a composite material that is generally difficult to reuse is used, which is not environmentally friendly. In particular, it is known that pasty chemicals are often formed into a paste by an organic solvent and have poor storage stability.

[0021] Further, Japanese Utility Model Publication No. 1-85732 discloses an automatic processor having means for charging a tablet-type antibacterial agent into a stabilizing solution. Since it does not cause any particular problem, it is not necessary to control the feeding, and this does not remind the treating agent replenishment controlling means, and the purpose is to preserve the liquid itself, so that it is not essential.

[0021] WO 91-07698 and WO 91-07699 disclose means for adding CD-3 or CD-4 as a solid and adding other components as a liquid agent as an activator. Is related to regeneration, in particular, an invention relating to low replenishment as close as possible to no overflow, and after removing bromide ions and chloride ions from a developing solution by an ion exchange resin, an alkaline agent activator or a solid or small amount which is a deficient component. It is a means for adding components without adding a thick color developing agent and increasing the volume.

In the present invention, the replenishment of the treating agent is carried out only by the operation of introducing the pre-divided and weighed solid treating agent into the treating tank, and by dissolving in the treating tank, the work of preliminarily dissolving the replenishing solution is eliminated and maintenance-free. The purpose of the present invention is completely different from that of the above invention, and the present invention cannot be presumed.

[0024]

SUMMARY OF THE INVENTION The first object of the present invention is to eliminate the liquid chemical that poses a transportation risk and a handling risk, and to enable the use of solid chemicals without complicated operations for the user. It is to achieve the practical application of a well-known automatic developing machine.

Secondly, there is an achievement of an automatic processor in which a fully automatic replenishment system is completed by eliminating the dissolution work of the concentration kit by the user himself.

Thirdly, there is the achievement of an automatic developing machine which is compact and eliminates many built-in replenishing tanks.

The fourth object is to achieve an automatic developing system with improved processing stability which eliminates the need for storing liquid replenisher.

The fifth object is to achieve a low pollution system in which the use of plastic bottles for liquids is eliminated and the use of plastic packaging materials is reduced.

[0029]

In order to solve the above problems, the present inventors have found that the above problems can be solved and achieved by the following constitution.

According to the first aspect of the present invention, the solid processing agent containing a plurality of components is a solid processing agent which is divided and weighed in advance in replenishment units or a fixed unit, and a batch solid processing agent in which all components are uniform. , An automatic development for silver halide photographic light-sensitive material having means for dropping the solid processing agent from the upper side to the lower side by utilizing the gravity stored in the processing tank and replenishing water supplying means for supplying water to the processing tank In the machine, the input amount of the solid processing agent per one time is in the range of 0.5 to 30 g, and the replenishing water supply of the replenishing water supplying means is supplied after being averaged according to the processing amount of the silver halide photographic light-sensitive material. It is characterized by having a replenishment water supply control means for controlling so as to control.

An automatic developing machine for silver halide photographic light-sensitive materials according to claim 2 comprises means for detecting and integrating the processing amount of the silver halide photographic light-sensitive material, and storage means for storing the integrated quantity information. It is characterized by having.

The automatic processor for silver halide photographic light-sensitive material according to claim 3 is characterized in that the unit of supply of replenishing water supplied by averaging is 2 ml to 100 ml. ..

An automatic processor for silver halide photographic light-sensitive material according to a fourth aspect is characterized in that the solid processing agent is a processing agent which is divided and weighed in advance by a moisture-proof material.

The automatic processor for silver halide photographic light-sensitive material according to claim 5 is characterized in that the solid processing agent is in the form of granules formed by a granulation step or tablets formed by tableting and is composed of uniform components. To do.

In the automatic processor for silver halide photographic light-sensitive material according to claim 6, the replenishing water is a chelating agent adding means,
Antifungal means selected from the group consisting of antifungal agent addition means, deionization treatment means, ultraviolet irradiation means, magnetic treatment means, ultrasonic treatment means, electrolytic sterilization means, silver ion release means, and air foaming means. Is characterized by.

An automatic developing machine for silver halide photographic light-sensitive materials according to claim 7 is characterized in that the solid processing agent previously divided and weighed contains all necessary components in a unit composed of a plurality of uniform tablets. .

[0037]

The inventors of the present invention have conducted a great deal of experiments on directly charging the solid processing agent into the tank, and have optimized the volume and weight of the solid processing agent added at one time so as not to change the photographic performance of each processing solution. I asked. This optimum kit amount depends on the size of the processing tank of the automatic processor, that is, the volume of the processing liquid, but by making good use of the characteristic of the solid chemical that is difficult to dissolve, the concentration will rapidly increase even if added at once. It has been found that the make-up water does not rise and can be poured in as the solution slowly dissolves, which has the advantage of creating extremely stable photographic performance. It turned out that it was a common sense that it had to be melted before use.

On the other hand, in Japanese Patent Laid-Open No. 4-213454, means for storing the solid processing agents divided into parts in separate storage boxes and inserting a certain amount of each part into a processing tank according to the processing amount is provided. It is disclosed. The disadvantage of this method is that if the particle size of each part is different, the density of solids in the storage box will change with the change rate that is different for each part over time, and it will not be possible to fractionate at a fixed rate. The liquid performance changes. It has been found that this fluctuation is a large and fatal drawback, especially under high humidity conditions. As a result of earnest research by the inventors,
It has been found that this drawback can be improved by granulating all the components to a certain particle size, and preparing them as a single agent or by separately weighing them in advance. Further, it was found that the solid processing agent which had been fractionally weighed in advance could completely eliminate this variation in the amount taken out.

The amount to be divided and weighed is generally 1 to 20 g for a color developing solution, 5 to 50 g for a fixing solution or a bleach-fixing solution,
Stabilizer is about 0.1 to 1 g, black and white developer is about 0.5 to 20 g, and solid chemicals in this range are put directly into the processing tank of a general small-sized developing machine and photographed even when slowly dissolving. Does not have any adverse effect on. This is because the solid treatment agent does not dissolve rapidly as described above, but dissolves slowly, so even if the amount added at one time is large, the composition is balanced with the composition that is consumed during processing and stable processing performance is exhibited. . It was also found that the photographic performance can be made constant by slowly injecting replenishing water in accordance with the dissolution. This was a surprising discovery that no one was aware of.

It has been discovered that this also has the great advantage that the insolubility phenomenon seen when dissolving in cold water does not appear. The insolubility phenomenon named by the inventors is a solidification phenomenon that occurs when the solid processing agent is added to cold water at once and slowly or hardly stirred.
At first glance, it means that the glass is in a vitrified state, and once vitrified, it has been found that it does not dissolve for a long time even with vigorous stirring.
On the other hand, in hot water dissolution at 25 ° C or higher, we found that even if solid chemicals were added more and more, each one dissolved in the order of addition.

Further, it has been found that when the replenisher is generally replenished by an automatic processor, the replenisher is cold water and the treatment temperature of the treatment tank is lowered to affect the processability. In particular, when the downsizing of the automatic developing machine is advanced today and the tank tank is downsized, the influence is great. However, the solid processing agent has a smaller heat capacity than the replenishing solution, and the temperature of the processing solution is less likely to change. Further, the inventors of the present invention have less fluctuation in the processing temperature in the automatic processor having the replenishing water supply means for supplying the replenishing water of the replenishing water supply means by averaging the supply amount of the replenishing water according to the processing amount of the photosensitive material. The present inventors have completed the present invention by discovering that there is no effect on the processability because there is little variation in the components.

Here, the supply amount of the replenishing water is averaged and supplied according to the processing amount of the light-sensitive material, and it means that a large amount of the replenishing water is not supplied all at once when the solid processing agent is added. It means that an averaged supply of makeup water is performed in the treatment tank. Specifically, the replenishment water supply required for the solid treatment agent after the solid treatment agent is supplied is continuously or relatively continuously supplied, and the necessary replenishment water amount is replenished in a plurality of times or continuously supplied. In this case, it means that water is supplied by averaging so that the amount of replenished water per minute is 7% or less with respect to the treatment tank. When supplementary water is supplied discontinuously, the amount of supplementary water per time is 100 ml or less, preferably 2 to 10
It is 0 ml. In the case of continuous feeding, preferably 0 per minute.
It is in the range of 05 to 5%, particularly preferably 0.01 to 4%. As a replenishment water supply means, there is a metering pump such as a bellows pump as a discontinuous one, and in the case of continuous replenishment, a peristaltic pump or the like is used, but the point is that averaged replenishment water is supplied. The replenishing water supply means may be any device as long as it satisfies the above conditions.

In the present invention, it is desirable that the replenishing water supplying means be similarly controlled by the processing amount detecting means of the photographic light-sensitive material necessary for controlling the feeding of the solid processing agent.
However, it should be emphasized that the replenishment water supplied by the replenishment water supply means is not water for dissolving the solid processing agent. That is, the solid processing agent is for supplementing the consumption component that was originally insufficient by the treatment, and the replenishing water is for the purpose of diluting the increased reaction suppressing component eluted by the treatment and keeping the photographic performance constant, The work is exactly the opposite. In the past, water happened to be used to dissolve chemicals, but the original purpose was, as mentioned above, the accumulation inhibitory component that elutes by the reaction while compensating for the water taken out by the photographic material and the water evaporated from the tank surface. It is for thinning. Therefore, although it can be controlled separately from the solid processing agent, it is preferable to control by the processing amount detecting means because the sensor can be omitted.

Therefore, in the present invention in which the solid chemical is directly added, the water which was not necessary in the prior art but was only necessary to dissolve the replenishing liquid becomes unnecessary, and as a result, the overflow is reduced. It turned out that the effect was great. Conventionally, there was a common sense that the replenisher should be dissolved, so we tried to make it as concentrated as possible to compensate the components as a replenisher, but if the concentration is higher than the solubility, the replenishment amount will be further reduced and it will be an environmental problem. Even though it was known that waste liquid could be reduced, the solubility of chemicals was a major obstacle and could not be achieved.
According to the present invention, the chemical has only the concentration of the tank liquid, there is no high-concentration state higher than that of the processing liquid in the processing tank, and only the necessary chemical can be supplied, so that it is possible to perform the supply without overflow at all.

However, as described above, replenishing water is used to reduce the accumulation of inhibitory components, particularly the concentration of halide ions in the developing solution and silver ions in the fixing solution and the bleach-fixing solution. Further, this replenishing water can independently supplement the water content of each processing solution brought out by the photographic material and lost by evaporation from the processing tank surface for the purpose of diluting these inhibitory components. It contributes to significantly increase processing stability.

Therefore, the control information used to supply the replenishing water is the processing amount (area) of the photographic material to be processed and the operating time, the temperature control time, the stop time, and the environmental temperature and humidity (relative humidity) of the installation place. , The dissolution rate of solid processing agents, etc., and if the amount of supplementary water added is controlled by these information, the chemical components in the processing tank can be managed in an ideal state, and in terms of photographic performance It can be said that it is a term management means. The reason is that, as the conventional low replenishment is advanced, the components of the treatment liquid are concentrated due to the effect of evaporation from each treatment tank, which has been a big problem. Generally, in order to correct the evaporation, the most preferable means is to dilute the replenisher and replenish it in a large amount.
This has the drawback of increasing overflow waste liquid and being unfavorable for the environment. Therefore, low replenishment has been promoted, and if replenishment liquid is used for evaporation correction, replenishment will occur even if it is not processed. And after all the ingredients come. Therefore, in the morning, it was common to replenish the water by adjusting the liquid level as much as the liquid level dropped, but this does not mean that the evaporated component is replenished with water, but the temperature changes and the volume increases. Only water was added to the reduced tank liquid, and no fundamental solution was achieved.

The correct evaporation correction is to ensure that the components do not change except for consumption of the photographic material, and the evaporation caused by the constant processing liquid temperature in the processing tank and the vapor pressure on the surface of the processing tank, whether processed or not. It is to replenish the water content according to the amount of evaporation.

That is, in the present invention, the supply of trapped water is performed for the following three purposes. In order to keep the concentration constant by diluting the increased accumulation harmful inhibition components eluted by the reaction of the processed photosensitive material, the moisture taken out by the processed photosensitive material or unnecessary chemicals brought in from the previous solution is removed. It is replenished for the purpose of diluting and diluting it, and for replenishing the water evaporated from the surface of the processing tank. The information necessary for the above purpose is detected, and the water preset by this information is detected. The supply software is controlled and executed. This means is a new means that has never existed before, and is made possible by the present invention.

It has been found that this water replenishing software of the present invention dramatically improves processing stability. In the present invention, the solid processing agent is divided and weighed in a predetermined amount in advance. Therefore, the processing by the automatic processor of the present invention has a high replenishment accuracy and exhibits extremely stable continuous processing performance. In the conventional replenisher supply replenishment system, replenishment is performed by a bellows pump, but the accuracy of this pump is not constant and is not suitable for precise replenishment control. On the other hand, in the case of the present invention, the solid processing agent is weighed and divided into a fixed amount at the chemical production factory, and the replenishment control is ON / OFF control whether or not the solid processing agent is fed. There is no. Therefore, the accuracy of chemical supply is remarkably high, and stable processing performance can be obtained by this. The solid processing agent of the present invention is a solid processing agent which is divided and weighed in advance or a batch solid processing agent containing at least two components. And, all components of this collective solid processing agent are granulated,
It is preferable to have a certain particle size. Further, the solid processing agent of the present invention may be any of powder, granules, tablets, pills and the like, and there is no problem in mixing these. The objective of this invention can be achieved even if a safe chemical such as water that does not become a dangerous substance is used in combination with a liquid. In order to better achieve this invention is a solid processing agent divided and weighed, tablets and pills for divided weighing are particularly preferred granules, in the case of powder an alkali-soluble film or plastic film,
It is desirable that the pieces are individually weighed after dividing and weighing with paper or the like.

That is, the tablets and pills themselves can be supplied as divided and weighed products with high accuracy, and in the powder or granule state, the effect of the present invention becomes more remarkable by separately packaging while separately weighing. Become. It has been found that tablets and pills can be moisture-proofed by coating them with a water-soluble moisture-proof polymer, and that powders and granules can be achieved by selecting moisture-proof materials for individual packaging materials.

The solid processing agent as referred to in the present invention means tablets, pills, granules, powders, etc. as described above, which have been subjected to a moisture-proof treatment as necessary, and are in the form of paste or slurry, or dangerous chemicals. However, it excludes those which are semi-liquid and have poor storage stability and are regulated with a risk of transportation, and these are not included in the solid processing composition of the present invention.

The collective solid treatment agent having at least two components according to the present invention is a solid treatment agent having a relatively large amount of 100 g or more, the components to be added are two or more components and uniformly mixed. means. This batch solid processing agent is preferably granulated by the same granulating means as that used in the production of the tablets. In particular, the particle size is preferably 50 to 5000 μm, and granules having a particle size of 50 to 1000 μm are particularly preferably used.

The powder used in the present invention refers to an aggregate of fine crystal grains. The granules referred to in the present invention are those obtained by adding a granulation step to powder, and refer to granules having a particle size of 50 to 5000 μm. The tablet referred to in the present invention refers to a powder or granules compression-molded into a given shape. Hereinafter, the present invention will be described in more detail.

Of the above solid processing agents, tablets are
It is preferably used because of high replenishment accuracy and easy handling. To solidify the photographic processing agent, a concentrated liquid or fine powder or granular photographic processing agent and a water-soluble binder are kneaded and molded, or the surface of the temporarily molded photographic processing agent is sprayed with the water-soluble binder. To form a coating layer, etc.
Arbitrary means can be adopted (Japanese Patent Application No. 2-135887 and 2-2031)
No. 65, No. 2-203166, No. 2-203167, No. 2-203168, No.
See No. 2-300409).

A preferable method for producing a tablet is to form a powdery solid processing agent by granulating and then performing a tableting step. There is an advantage that the solubility and the storability are improved and the photographic performance becomes stable as compared with the solid processing agent formed by the tableting step by simply mixing the solid processing agent components. Granulation means for tablet formation include rolling granulation, extrusion granulation, compression granulation,
Known means such as disintegration granulation, stirring granulation, fluidized bed granulation, spray drying granulation and the like can be used. For tablet formation, the average particle size of the obtained granules is 100 to 800 μm, because when the granules are mixed and compressed under pressure, nonuniformity of the components, so-called segregation does not easily occur. It is preferable to use one, and more preferably 200 to 750 μm. Further, the particle size distribution is preferably such that 60% or more of the granulated product particles have a deviation of ± 100 to 150 μm. When compressing the obtained granulated product under pressure, a known compressor such as a hydraulic press, a single-shot tableting machine, a rotary tableting machine, or a preketching machine can be used. The solid processing agent obtained by compression under pressure can have any shape, but from the viewpoint of productivity, handleability, or from the problem of dust when used on the user side, a cylindrical type, a so-called tablet is used. preferable.

More preferably, at the time of granulation, the above-mentioned effect becomes more remarkable by separately granulating each component, for example, an alkali agent, a reducing agent, a bleaching agent, a preservative and the like. Alternatively, the effect described above becomes more remarkable by using a multilayer tablet.

A means for producing a tablet processing agent is described in, for example, Japanese Patent Laid-Open No.
51-61837, 54-155038, 52-88025, British patent 1
It can be produced by a general method described in the specification such as 213808, and further, the granule treating agent is, for example, JP-A-2-09042,
It can be produced by the general means described in the specifications such as 2-109043, 3-39735 and 3-39739. Further, the powder processing agent is, for example, JP-A-54-133332, British Patent 725892.
No. 7,298,62 and German Patent No. 3738361, and the like. For example, in the case of a three-layer tablet, the means for producing a multi-layer tablet is "Development of Pharmaceuticals Volume 11 P78.
It can be manufactured by referring to the means described in ".about.79".

[0058] The bulk density of the solid processing agent, and in view of its solubility, if a tablet from the viewpoint of the effect of interest 1.0g / cm ³ ~2.5g / cm ³ is preferably 1.0 g / cm of the present invention ^{When it is} larger than ³ , the strength of the obtained solid is more preferable, and when it is smaller than 2.5 g / cm ³ , the solubility of the obtained solid is more preferable. When the solid processing agent is granules or powder, the bulk density is preferably 0.40 to 0.95 g / cm ³ . Solid processing agents used in this invention include color developing agents, black and white developing agents, bleaching agents, fixing agents, bleach-fixing agents,
Although it is used as a photographic processing agent such as a stabilizer, it is a color developing agent that has a large effect of stabilizing the photographic performance of the present invention. The black and white developing agents, color developing agents, bleaching agents, bleach-fixing agents and stabilizers can be excluded from the regulation of liquid dangerous substances.

According to the embodiment of the present invention, it is most preferable that all the processing agents are solid processing agents, but it is preferable to solidify at least the color developing agent. That is, since the color developer component contains a large number of components that cause a chemical reaction with each other and also contains a harmful component, the effect of the present invention is most prominently exhibited. More preferably, in addition to the color developing agent, a bleach-fixing agent, or a bleaching agent and a fixing agent are made into a solid processing agent. Conventionally, these are liquid packaging kits, which pose a problem of transportation risk.

It is within the scope of the present invention to solidify only one part of a certain treating agent in the solid treating agent used in the present invention, but preferably all components of the treating agent are solidified. is there. It is desirable that each component be molded as a separate solid processing agent and packaged in the same manner. It is also desirable that the individual components are packaged in the order in which they are periodically added repeatedly in a package. It is preferable to add all of the processing agents to be replenished to each processing tank as solid processing agents according to the processing amount information. When replenishment water is required, it is replenished based on the throughput information or other replenishment water control information. In this case, the liquid to be replenished in the processing tank can be only replenishing water. That is, when there are two or more types of processing tanks that need to be replenished, only one tank is required to store the replenishing liquid by sharing the replenishing water, and the automatic developing machine can be made compact. In particular, it is preferable to place one replenishing water tank on the outside in order to make the automatic developing machine compact.

In the case of solidifying the color developing agent, it is preferable that all of the alkaline agent, the color developing agent and the reducing agent are solid processing agents, and in the case of tablets, at least 3 agents or less, most preferably 1 agent. It is a preferred embodiment of the solid processing agent used. When two or more agents are divided into solid processing agents, it is preferable that the plurality of tablets and granules be packed in the same package. The following materials can be used for moisture-proof packaging of tablets and pills.

As the synthetic resin material, polyethylene (either high pressure method or low pressure method), polypropylene (either unstretched or stretched), polyvinyl chloride, polyvinyl acetate, nylon (stretched or unstretched), polychlorinated Vinylidene, polystyrene, polycarbonate, vinylon, eval, polyethylene terephthalate (PET), other polyester, hydrochloric acid rubber, acrylonitrile butadiene copolymer, epoxy-phosphoric acid resin (JP-A-63-63037)
And the polymers described in JP-A-57-32952). Alternatively, pulp may be used. These are usually laminated and adhered to the film, but may be applied as a coating layer.

Further, it is more preferable to use various gas barrier films such as using aluminum foil or aluminum vapor deposition synthetic resin between the above synthetic resin films. The total oxygen transmission rate of these laminated films is 50 ml / m ² 24 hr /
atm or less (at 20 ℃ 65% RH), more preferably 30 ml / m ² 24 hr
It is preferably less than / atm. The total thickness of these laminated films is 1 to 2000 μm, more preferably 10 to 1000 μm.
m, more preferably 50 to 1000 μm. The above synthetic resin film may be a single layer (polymer) resin film, or may be a laminate of two or more (polymer) resin films.

Examples of the one-layer polymer resin film satisfying the conditions of the present invention include (1) polyethylene terephthalate (PET) having a thickness of 0.1 mm or more, and (2) acrylonitrile butadiene copolymer having a thickness of 0.3 mm or more. (3) Hydrochloric acid rubber having a thickness of 0.1 mm or more, and the like. Among them, polyethylene terephthalate is excellent in alkali resistance and acid resistance, and thus can be suitably used in the present invention.

Next, as the laminated polymer resin film which meets the conditions of the present invention, for example, (4) PET / polyvinyl alcohol / ethylene copolymer (Eval) / polyethylene (PE), (5) stretched polypropylene ( OPP) / Eval / PE, (6) Unstretched polypropylene (CPP) / Eval / PE, (7) Nylon (N) / Aluminum foil (Al) /
PE, (8) PET / Al / PE, (9) cellophane / PE
/ Al / PE, (10) Al / paper / PE, (11) PET / PE
/ Al / PE, (12) N / PE / Al / PE, (13) paper / P
E / Al / PE, (14) PET / Al / PET / polypropylene (PP), (15) PET / Al / PET / high density polyethylene (HDPE), (16) PET / Al / PE / low density polyethylene (LDPE) ), (17) Eval / PP,
(18) PET / Al / PP, (19) paper / Al / PE, (20) P
E / PVDC Coated Nylon / PE / Ethyl Vinyl Acetate Polyethylene Condensate (EVA), (21) PE / P
VDC Coated N / PE, (22) EVA / PE / Aluminum Deposition Nylon / PE / EVA (23) Aluminum Deposition Nylon / N / PE / EVA (24) OPP / PVDC Coated N / PE, (25) PE / PV
DC coat N / PE, (26) OPP / Eval / LDP
E, (27) OPP / Eval / CPP, (28) PET / Eval / LDPE, (29) ON (stretched nylon) / Eval / LDPE, (30) CN (unstretched nylon) / Eval /
There are LDPE and the like, and among them, the above (20) to (30) are preferably used.

As a more specific structure of the packaging material, if the side in contact with the treating agent is the inner surface, PE / mainly paperboard / PE / Al / epoxy-phosphoric acid resin layer / polyester resin in this order from the inner surface. Layer / PE PE / K-nylon / PE or adhesive / Al / PE /
Paperboard / PE, PE / vinylon / PE or adhesive / Al / PE / paperboard / PE PE / vinylidene chloride / PE or adhesive / Al / PE
/ Paperboard / PE PE / Polyester / PE or Adhesive / Al / PE /
Paperboard / PE Polypropylene / K-Nylon / Polypropylene / Al
/ Polypropylene / paperboard / polypropylene etc.
As a means for moisture-proof packaging of tablets and granules, there are 4-way seal, 3-way seal stick (pillow package, gusset package) PTP cartridge.

The four-way seal, three-way seal, and stick (pillow, gusset) packaging are different in the form, and the above materials are used, but when used in the peel-open system, a sealant agent is laminated to provide peel-open suitability. . This peel-open method generally includes a cohesive failure method, an interfacial peeling method, and an interlayer peeling method.

The cohesive failure method is an adhesive called hot melt, which is used as a sealant in a heat-seal lacquer, and peels off due to internal cohesive failure of the sealant layer at the time of opening.

The surface-active peeling method is a method of peeling at the interface between films, in which the sealing film (sealant) and the adherend are not completely fused and can be peeled with an appropriate strength. The sealant is a film in which an adhesive resin is mixed, and polyethylene, polypropylene or a copolymer thereof, a polyester type, or the like can be selected depending on the material of the adherend. Further, the delamination method is to peel the sealant between the layers of the laminate film by using a multilayer coextrusion film such as a laminate film.
In the peel-open method using the film of the present invention, the interlayer peeling method or the interface peeling method is preferable.

Since such a sealant is thin,
Usually, other films such as polyethylene, polypropylene, polystyrene, polycarbonate, polyester (polyethylene terephthalate), polyvinyl chloride, nylon, eval, aluminum are laminated and used, but considering moisture resistance, environmental friendliness and matching with contents. Polyethylene, polypropylene, polyester, EVAL and the like are preferable. In consideration of printability, the outermost surface is preferably unstretched polypropylene polyester, paper or the like.

Examples of the sealant film include CMPS film manufactured by Tohcello, Diffran PP-100 and PS-300 manufactured by Dainippon Ink and LTS film manufactured by Toppan Printing, Sunseal FR manufactured by San-A Chemical, and Sunseal MS. As a type laminated with polyester, there are Declan C-1600T, C-1602T and the like. PTP is a type of blister packaged PV
It is a packaging form in which a solid processing agent is put into a sheet of C, CPP or the like and heat-sealed with an aluminum sealing material. Environmentally, PVC is not used as a forming material, and recently A-PET is used.
Highly moisture-proof PP (eg TAS-1130, TAS-2230, TA
S-3230: Taisei Kako Co., Ltd. is preferably used.

When the treating agent is packaged or bound or coated with a water-soluble film or a binder, the water-soluble film or the binder may be polyvinyl alcohol, methyl cellulose, polyethylene oxide, starch, polyvinyl pyrrolidone, Hydroxypropyl cellulose type, pullulan type, dextran type and gum arabic type,
Polyvinyl acetate-based, hydroxyethyl cellulose-based, carboxyethyl cellulose-based, carboxymethyl hydroxyethyl cellulose sodium salt-based, poly (alkyl) oxazoline-based, polyethylene glycol-based film or binder is preferably used, among these, In particular, polyvinyl alcohol type and pullulan type are more preferably used from the viewpoint of the effect of coating or binding.

The preferred polyvinyl alcohol is a very good film-forming material and has good strength and flexibility under most conditions. Commercially available polyvinyl alcohol compositions cast as films vary in molecular weight and degree of hydrolysis, but have molecular weights of about 10,000 to about 10,000.
It is preferably 0. The degree of hydrolysis is the rate at which the acetic acid ester group of polyvinyl alcohol is replaced with a hydroxyl group. For film applications, the hydrolysis range is usually about 70% to 100%. Thus, the term polyvinyl alcohol usually includes polyvinyl acetate compounds.

The methods for producing these water-soluble films are described in, for example, JP-A-2-124945, JP-A-61-97348, and JP-A-60-15824.
5, JP-A-2-86638, JP-A-57-117867, JP-A-2-7
5650, JP-A-59-226018, 63-218741 and 54-1
It is produced by a general method as described in Japanese Patent No. 3565. Further, as these water-soluble films, those commercially available under the names of Solbron (manufactured by Aicello Chemical Co., Ltd.), Hi-Selon (manufactured by Nigo Film Co., Ltd.) or Pullulan (manufactured by Hayashibara Co., Ltd.) can be used. Also, Chris Craft Industries
ries) Inc. The 7-000 series polyvinyl alcohol films available from the MONO-SOL division of the Company melt at water temperatures of about 34 degrees F to about 200 degrees F,
It is harmless and exhibits a high degree of chemical resistance, and is particularly preferably used.

The thickness of the above water-soluble film is preferably 10 to 120 μ, particularly 15 to 80 μ from the viewpoints of storage stability of the solid processing agent, dissolution time of the water-soluble film and crystal precipitation in an automatic processor. Preferred, especially 20
Those having a size of -60 μm are preferably used. Further, the water-soluble film is preferably thermoplastic. This not only facilitates heat sealing and ultrasonic welding, but also
This is because the covering effect is also exhibited more favorably. Further, the tensile strength of the water-soluble film is preferably 0.5 × 10 ⁶ to 50 × 10 ⁶ kg / m ² , particularly preferably 1 × 10 ^{6 to} 25 × 10 ⁶ kg / m ² , and particularly preferably 1.5 × 10 ⁶ to 10 × 10 ⁶ kg / m ² is preferred. These tensile strengths are measured by the means described in JIS Z-1521.

Further, the photographic processing agent packaged or bound or coated with a water-soluble film or a binding agent is used in storage, transportation, and handling during storage, transportation, and handling. Humidity in the atmosphere such as high humidity, rain, and fog, and water. It is preferably packaged in a moisture-proof packaging material in order to prevent damage from sudden contact with water by splashing or wet hands, and the moisture-proof packaging material has a film thickness of 10 to 150 μm.
The preferred film is a moisture-proof packaging material such as polyethylene terephthalate, polyethylene, a polyolefin film such as polypropylene, kraft paper which can have a moisture resistance effect with polyethylene, wax paper, moisture-resistant cellophane, glassine, polyester, polystyrene, polyvinyl chloride, polyvinyl chloride. It is preferably at least one selected from vinylidene, polyamide, polycarbonate, acrylonitrile-based and metal foils such as aluminum, and a metallized polymer film, or a composite material using these. Further, in the practice of the present invention, it is also preferable to use a degradable plastic, particularly a biodegradable or photodegradable plastic, as the moisture-proof packaging material.

Examples of the biodegradable plastics include those made of natural polymers, polymers produced by microorganisms, synthetic polymers having good biodegradability, blending of biodegradable natural polymers with plastics, and photodegradable plastics are ,
Examples thereof include a group that is excited by ultraviolet rays and has a group that is linked to cleavage in the main chain. Further, other than the above-mentioned polymers, those having two functions of photodegradability and biodegradability at the same time can be favorably used. The specific representative examples are as follows.

Examples of biodegradable plastics include natural polymer polysaccharides, cellulose, polylactic acid, chitin, chitosan, polyamino acids, and modified products thereof. Microbial polymers PHB-PHV (3-hydroxybutyrate and 3-hydroxyvalerate (Copolymer with rate) as a component "Biopo
l ", microbial-produced cellulose and other biodegradable synthetic polymers polyvinyl alcohol, polycaprolactone, etc. or their copolymers or mixtures Blending biodegradable natural polymer into plastics As a biodegradable natural polymer, , Starch, and cellulose, which have shape-disintegrating properties in addition to plastic.

Examples of the photodegradability include the introduction of a carbonyl group for photodisintegration and the addition of an ultraviolet absorber to accelerate the disintegration. For such degradable plastics, see “Science and Industry”, No. 64.
Volume No. 10, pp. 478-484 (1990), "Functional Materials" July 1990, pp. 23-34, etc. can be used. Also, Biopol (manufactured by ICI), Eco (eco) (manufactured by Union Carbide), Ecolite (ecolight) (EcoPlas).
tic), Ecostar (Ecostar) (St.
Lawrence Starch), Knuckle P
Commercially available decomposed plastics such as (manufactured by Nippon Unicar Co., Ltd.) can be used. The moisture-proof packaging material preferably has a moisture permeability coefficient of 10 g · mm / m ² 24 hr or less, more preferably 5 g · mm / m ² 24 hr or less.

In the present invention, as the supply means for supplying the solid processing agent to the processing tank, for example, when the solid processing agent is a tablet, JP 63-137783 A, JP 63-97522 A, JP 1 Although there are known means such as Japanese Patent Publication No. 85732, any means may be used as long as it has at least the function of supplying tablets to the processing tank. When the solid processing agent is granules or powder, the gravity drop method described in JP-A-62-81964, JP-A-63-84151, JP-A-1-292375, and JP-A-63-105159.
No. 63-195345, etc., the method using a screw or screw is a known means, but is not limited thereto.

However, the preferable means is, as the supply means for supplying the solid processing agent to the processing tank, for example, a predetermined amount of the solid processing agent which has been previously weighed and divided and packaged is opened according to the processing amount of the photosensitive material, and the package is opened. Means of taking out can be considered. Specifically, the solid processing agent is sandwiched and housed in a package composed of at least two packaging materials by a predetermined amount, preferably a replenishment amount for one time, and the package is separated in two directions or the package A part of it is opened so that it can be taken out. The solid processing agent that can be taken out can be easily supplied to the processing tank having the filtering means by spontaneous dropping. A predetermined amount of the solid processing agent is housed in a package that is divided and sealed so that air permeability between the solid processing agent and the adjacent solid processing agent is blocked. Therefore, moisture resistance is guaranteed unless the package is opened.

As an embodiment, it is conceivable that a package composed of at least two packaging materials sandwiching the solid processing agent is adhered or adhered to each other at their contact surfaces so that the periphery of the solid processing agent can be separated. . By pulling the respective packaging materials sandwiching the solid processing agent in different directions, the closely contacted or bonded contact surfaces are separated, and the solid processing agent can be taken out.

As another embodiment, it is conceivable that at least one of the packages made of at least two packaging materials can be opened by an external force so as to sandwich the solid processing agent. The term "opening" as used herein means a cut or break that leaves a part of the packaging material. As the opening means, forcibly extruding the solid processing agent by applying a compressive force from the packaging body on the unopening side to the packaging body that can be opened through the solid processing agent, or on the packaging body on the openable side. It is considered that the solid processing agent can be taken out by making a cut with a sharp member.

The supply start signal is obtained by detecting the processing amount information. Further, the driving means for separating or unsealing operates based on the obtained supply start signal. The supply stop signal is obtained by detecting the information that the supply of the predetermined amount is completed. Further, based on the obtained supply stop signal, the driving means for separating or unsealing is controlled to stop. The solid processing agent supply means has a control means for charging a fixed amount of the solid processing agent in accordance with information on the processed amount of the light-sensitive material, which is an important requirement in the present invention. That is, in the automatic processor of the present invention, it is necessary to keep the concentration of components in each processing tank constant and to stabilize the photographic performance. The processing amount information of the silver halide photographic light-sensitive material is the processing amount of the silver halide photographic light-sensitive material processed by the processing liquid, the processing amount of the processed silver halide photographic light-sensitive material, or the silver halide photograph during the processing. It is a value proportional to the processing amount of the light-sensitive material, and indirectly or directly indicates the reduction amount of the processing agent in the processing liquid. It may be detected before or after the photosensitive material is carried into the processing liquid, or at any timing during immersion in the processing liquid. It may also be the amount of the light-sensitive material printed by the printer. Furthermore, it may be the concentration of the treatment liquid contained in the treatment tank or the change in the concentration. Further, it may be the amount of the treatment liquid which is discharged to the outside after drying.

The solid processing agent of the present invention may be placed in a processing tank, but preferably, it is connected to a processing section for processing a light-sensitive material, and a processing solution flows between the processing section and the processing section. It is preferable that the structure is such that the dissolved components move to the treatment section because there is a certain amount of treatment liquid circulation between the treatment section and the treatment section. The solid processing agent is preferably added to the temperature-controlled processing liquid.

Generally, since the temperature of an automatic processor is controlled, the temperature of the processing solution is controlled by an electric heater. A heat exchange section is provided in an auxiliary tank connected to a processing tank as a processing section, and a heater is installed to replenish the tank. Is equipped with a pump that feeds the liquid from the processing tank in a constant circulation amount and keeps the temperature constant. And usually mixed in the processing liquid,
A filter is arranged for the purpose of removing the crystalline foreign matter generated by crystallization, and plays a role of removing the foreign matter. The most preferable means is to put the solid processing agent in a place where the temperature is adjusted, such as a place communicating with the processing section such as this auxiliary tank. This is because the insoluble component in the charged processing agent is blocked from the processing section by the filter section, and the solid content can be prevented from flowing into the processing section and adhering to the photosensitive material.

Further, when the treatment agent input portion is provided in the treatment tank together with the treatment portion, it is preferable to devise a shield or the like so that the insoluble portion does not come into direct contact with the film or the like. As for the material of the filter, the filtering device, etc., all of those used for general automatic developing machines can be used in the present invention, and the special structure and material do not influence the effect of the present invention. The present invention eliminates the need for a tank or the like for storing the replenisher by adding the solid processing agent to the processing tank, which makes the automatic developing machine compact, and when the circulating means is provided, the solubility of the solid processing agent is extremely high. Will be good.

The antifungal means of the refill water tank of the present invention will be described. When the replacement rate in the replenishment tank is reduced and the residence time of water is prolonged, scales are generated, and the water is putrefused for 2-3 weeks to cause a bad odor. Also, if the generated water stains are replenished as they are, they will adhere to the surface of the photosensitive material, causing uneven development in the case of a color developing tank, poor desilvering in the case of a desilvering tank, and dirt in the case of a stable tank. There is a big problem that the product value of the finished product is significantly reduced. Therefore, in order to remove this scale, it has to be washed regularly, which is very time-consuming and maintenance-free. Further, if it is mixed in the processing tank and cannot be removed by the filter, there are rollers for transportation and the like, and cleaning them is an extremely difficult work. Therefore, in order to be maintenance-free, in the present invention, the water replenishment tank has a means for preventing mold and for preventing generation of microorganisms. This preventing means is selected from the group consisting of chelating agent adding means, antifungal agent adding means, deionizing treatment means, ultraviolet irradiation means, magnetic treatment means, ultrasonic treatment means, electrolytic sterilization means, silver ion releasing means and air foaming means. Can be achieved by at least one means.

These means will be specifically described.

The chelating agent and bactericidal agent used as the antifungal means in the present invention are L. E. West "W
ater Quality Criteria ”Ph
otSci. and Eng. , Vol9, no. 6,
398 (1965), M .; E. Each. "Micro
biological Gro wt in Mot
ion-Picture Processing "SM
PTE Journal, vol. 85. mar. (197
6), R. O. Deegan, “Photoproce
ssingu Wash Water Biocide
s "J.Imaging Tech.vol.10, N
o. 6, 239 Dec (1984), JP-A-57-8542,
The compounds described in 58-105145, 57-157244, 62-220951 and the like can be used.

Preferred chelating agents are ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1-hydroxyethylidene-1,1-diosphonic acid, ethylenediaminetetra (methylenephosphonic acid).

[0092]

[Chemical 1] The bactericides are preferably phenol compounds, thiazole compounds and benztriazole compounds.
Specifically, 1,2-benzisothiazolin-3-one, 2-methyl-4-osothiazolin-3-one, 2-octyl-4-isothiazolin-3-one, 5-chloro-2
-Methyl-4-isothiazolin-3-one, 0-phenylfelsodium and benztriazole are mentioned as preferred compounds.

If these compounds are packaged in a package, it is preferable that they are in the form of tablets, and if they are divided and weighed in advance, it is preferable that they are individually packaged in an amount to be added at one time. . Means for adding these may be added by hand by the pharmacist, but it is preferable that the solid processing agent supply device of the present invention is installed to add by hand, and more preferably, the replenishment tank is equipped with a detector. From the viewpoint of maintenance-free, it is preferable to add water automatically when the tank is replenished with water to a certain amount.

The means for modifying water with the ion exchange resin of the present invention can be implemented based on the means described in JP-A-61-131632. As the ion exchange resin, various known cation exchange resins (strongly acidic cation exchange resin, weakly acid live cation exchange resin) and various anion exchange resins (strongly basic anion exchange resin) described in Public Technical Report, Official Technical Number 90-473, etc. ) And these can be used alone or in combination. Normally, strong acidic H-type cation exchange resin and weak basic O
It is preferable to use an H-type anion exchange resin. It may be attached to a replenishment tank or it may be reformed and brought to another location.

Preferred ion exchange resins for strong acid used in the present invention are DIAION SK1B, SK102, SK104 and SK10.
6, SK110, SK112, SK116 Mitsubishi Kasei (manufactured) As preferred OH type strongly basic anion exchange resin, DIAION PA406, PA408, PA412, PA416,
There is PA418 Mitsubishi Kasei (manufactured by).

The means for irradiating with ultraviolet rays of the present invention can be implemented by the means described in JP-A-60-263939. As the ultraviolet irradiation device, a product manufactured by Kindai Bio Research Institute (headquarters Kobe City) is small and can be preferably used. The means for applying the magnetic field of the present invention can be implemented by the means described in JP-A-60-263939. The means for applying ultrasonic waves of the present invention can be implemented by the means described in JP-A-60-263940. The means for applying the electrolysis of the present invention can be carried out by the means described in JP-A No. 3-22468. Ag of this invention
The means for releasing ions include a means for putting a silver foil or a silver plate in the water replenishment tank, a means for coating the inner wall with silver, and a means for putting a silver ion releasing compound. A preferred silver ion-releasing compound is BioSure SGorS.
It is very effective to coat or insert the inner wall of the tank using GD (Kinki Pipe Giken). The air blowing means of the present invention may be a very simple means for blowing bubbles into the refill water tank, and it is appropriately selected according to the size of the refill water tank. From the viewpoints of compactness and economy, these antifungal means are preferable, and more preferable are effective.

[0097]

【Example】

(Example 1) An automatic developing machine to which the present invention can be applied (hereinafter,
An example of an automatic processor) will be described with reference to the drawings.
FIG. 1 is a schematic diagram of a printer processor in which an automatic developing machine A and a photo printing machine B are integrally configured.

In FIG. 1, in the lower left part of the photographic printing apparatus B, there is set a magazine M containing photographic paper, which is an unexposed silver halide photographic photosensitive material, in a roll form. The photographic printing paper pulled out from the magazine is cut into a predetermined size via the feed roller R and the cutter section C to become a sheet-shaped printing paper. The sheet-shaped printing paper is conveyed by the belt conveying means B, and the image of the original image O is exposed in the exposure section E. The exposed sheet-shaped printing paper is further conveyed by a plurality of pairs of feed rollers R and introduced into the automatic developing machine A.
In the automatic developing machine A, the sheet-shaped photographic papers are color developing tank 1A, bleach-fixing tank 1B, stabilizing tanks 1C, 1D, 1 which are processing tanks.
It is sequentially conveyed in E (substantially three tanks) by roller conveying means (reference symbol None), and color development processing, bleach-fixing processing, and stabilization processing are performed respectively. The sheet-shaped printing paper that has been subjected to each of the above processes is dried in the drying unit 35 and discharged to the outside of the machine.

The alternate long and short dash line in the figure indicates the transport path of the silver halide photographic light-sensitive material. In the embodiment, the light-sensitive material is introduced into the automatic developing machine A in a cut state, but it may be introduced into the automatic developing machine in the form of a strip. In that case, if an accumulator for temporarily retaining the photosensitive material is provided between the automatic developing machine A and the photoprinting machine B, the processing efficiency is improved. Further, it goes without saying that the automatic developing machine according to the present invention may be configured integrally with the photo printing machine B or may be a single automatic developing machine. Further, it goes without saying that the silver halide photographic light-sensitive material processed by the automatic developing machine according to the present invention is not limited to the exposed printing paper, and may be an exposed negative film or the like. Further, as an explanation of the present invention, a color developing tank, a bleach-fixing tank,
Although the present invention is carried out on a substantially three-tank automatic developing machine having a stabilizing tank, the present invention is not limited to this. However, the present invention can be applied.

FIG. 2 is a schematic view of a color developing tank 1A which is a processing tank in the I-I cross section of the automatic developing machine A of FIG. The bleach-fixing tank 1B and the stabilizing tanks 1C, 1D, and 1E have the same configuration as the color developing tank 1A. Therefore, when the processing tank 1 is described below, the color developing tank 1A, the bleach-fixing tank 1B, and the stable tank are stable. Here, all of the tanks 1C, 1D, and 1E are referred to. In the figure, in order to make the configuration easier to understand,
Conveying means for conveying the photosensitive material and the like are omitted. Also,
In this example, the case where the tablet 13 is used as the solid processing agent will be described.

The processing tank 1 is a processing section 2 for processing a photosensitive material.
And a solid processing agent feeding section 11 for supplying tablets 13 integrally provided on the outside of the partition wall forming the processing section. The processing section 2 and the solid processing agent feeding section 11 are partitioned by a partition wall 12 having a communication window formed therein, so that the processing liquid can flow. Further, since the section 14 for receiving the treatment agent is provided in the feeding section 11, it does not move to the treatment section 12 in a solid state. The cylindrical filter 3 is a solid processing agent charging section.
It is provided below 11 so as to be replaceable, and has a function of removing insoluble matter such as paper waste in the processing liquid. In the filter 3, a circulation pump 5 (circulation means) is provided through a circulation pipe 4 which penetrates a lower wall of the solid processing agent feeding part 11.
It communicates with the suction side of.

The circulation system is composed of the circulation pipe 4 forming the liquid circulation passage, the circulation pump 5, the processing tank 1 and the like. The other end of the circulation pipe 4 communicating with the discharge side of the circulation pump 5 penetrates the lower wall of the processing unit 2 and communicates with the processing unit 2. With such a configuration, when the circulation pump 5 is operated, the treatment liquid is sucked from the solid treatment agent input unit 11 and discharged to the treatment unit 2 so that the treatment liquid mixes with the treatment liquid in the treatment unit 2 and the solid treatment agent is again supplied. The circulation that enters the input unit 11 is repeated. The flow rate of this circulating flow is 1
The flow rate is preferably 0.1 (rotation = circulation amount / tank volume) or more with respect to the tank volume per minute, and more preferably 0.5 to 2.0 rotations. Further, the circulation direction of the processing liquid is not limited to the direction shown in FIG. 2 and may be the opposite direction.

The waste liquid pipe 6 is for overflowing the processing liquid in the processing section 2, and keeps the liquid surface level constant, as well as the components brought into the photosensitive material from other processing tanks and the photosensitive material. The component leaching from the material is stored,
Helps prevent the increase. The rod-shaped heater 7 penetrates the upper wall of the solid processing agent feeding section 11 and passes through the solid processing agent loading section.
It is arranged so as to be immersed in the treatment liquid in 11. The heater 7 heats the processing liquid in the processing tank 1.
In other words, it is a temperature adjusting means for maintaining the treatment liquid in the treatment tank 1 in a temperature range suitable for treatment (for example, 20 to 55 ° C.).

The processing amount information detecting means 8 is provided at the entrance of the developing machine and is used for detecting the processing amount of the photosensitive material to be processed. The processing amount information detecting means 8 has a plurality of detecting members arranged in the left-right direction and functions as an element for detecting the width of the photosensitive material and for counting the detected time. Since the conveying speed of the photosensitive material is mechanically preset, the processing area of the photosensitive material can be calculated from the width information and the time information. The processing amount information detecting means may be any one capable of detecting the width and the transport time of the photosensitive material such as an infrared sensor, a micro switch and an ultrasonic sensor. Further, in the case of a device capable of indirectly detecting the processed area of the photosensitive material, for example, in the case of a printer processor as shown in FIG. 1, the amount of the photosensitive material that has been printed, or
Alternatively, the number of processed light-sensitive materials having a predetermined area may be detected. Further, the detection timing is before the treatment in this example, but may be after the treatment or during the immersion in the treatment liquid (in such a case, the position where the treatment amount information detecting means 8 is provided). Can be appropriately changed to a position that can be detected after processing or a position that can be detected during processing). Further, as the detected information, the processing area of the photosensitive material is described in the above description,
The value is not limited to this, and may be any value that is proportional to the processing amount of the photosensitive material to be processed, processed, or being processed, and may be the concentration of the processing liquid contained in the processing tank or the change in the concentration. It may be. Further, it is not necessary to provide the processing amount information detecting means 8 for each of the processing tanks 1A, 1B, 1C, 1D, 1E, but it is preferable to provide one for each automatic developing machine.

The treatment agent supply means 17 for introducing the solid treatment agent stored in the cartridge 15 as the storage means into the processing tank is
A cartridge (15), which is arranged above the filtering section (section) (14) and encloses tablets (13) that are solid processing agents, and an extruding member (10) configured to extrude one or more tablets (13). The processing agent supply means 17 is a processing agent supply control means 9 described later.
The tablet 13 which has been on standby is extruded by the extruding member 10 in association with the supply signal which is controlled by the processing agent supply control means 9 and the tablet 13 is filtered by the solid processing agent injection section 11 (section). Supply to 14. In the invention of the present application, the solid processing agent 13 is supplied to the filtering section (section) 14 in the solid processing agent receiving section 11, but it may be supplied anywhere as long as it is in the processing tank 1. In the present invention, it is only necessary that the solid processing agent can be dissolved using the processing liquid, and it is necessary to surely add the component according to the processing amount information of the photosensitive material and to keep the processing characteristics of the processing liquid in the processing tank 1 constant. However, it is more preferable that the solid processing agent is supplied into the circulation path of the processing liquid. In addition, the treatment agent supply means 17 is configured so that moisture in the treatment tank of the automatic processing machine and humidity in the outside air, and scattered treatment liquid do not come into contact with the solid treatment agent before being supplied to the treatment tank. Is preferred.

The filtering means (section) 14 is a solid processing agent charging section.
An insoluble component by the tablet 13 which is dipped in the treatment liquid in 11 and supplied by the treatment agent supplying means 17, for example, an insoluble component mixed in the tablet 13, and a tablet formed by disintegrating the tablet 13.
A lump of 13 or the like that removes not only the tablets 13 but also those derived from the solid processing agent that cause scratches on the resulting image 12 or cause insufficient processing of the adhered areas, etc. Is. The filtering means (section) 14 is made of resin. The filtering means (section) 14 is not essential to be provided in the solid processing agent feeding section 11, and the tablets 13 supplied by the processing agent supplying means 17 are the photosensitive material conveying path shown in FIG. 1 or the processing section. It may be added to the treatment liquid in No. 2.

The processing agent supply control means 9 is a processing agent supply means.
When the processing amount information (processing area in this embodiment) of the photosensitive material detected by the processing amount information detecting means 8 reaches a predetermined constant value, the processing agent supplying signal is sent to the processing agent supplying means 17. Is to be emitted. The processing agent supply control means 9 may control the processing agent supply means 17 so as to supply the required amount of processing agent to the solid processing agent input part 11 in accordance with the processing amount information. The processing amount of the photosensitive material processed by the processing amount information detecting means 8 is detected, and the replenishing water supplying means 18 supplies the replenishing water to the filtering section 14 by the metering pump 19.

Next, the operation of the present invention will be described with reference to FIG. The processed amount information of the exposed photosensitive material is detected by the processed amount information detecting means 8 at the entrance of the automatic developing machine A. When the cumulative area of the photosensitive material to be processed reaches a predetermined area in accordance with the processing amount information detected by the processing amount information detecting means 8, the processing agent supply control means 9 and the processing agent supply means 17 and supplementary water. A supply signal is issued to the supply means 18. Upon receiving the supply signal, the processing agent supply means 17 pushes out the tablets 13 with the extrusion member 10 and supplies the tablets 13 to the filtering means (section) 14 in the solid processing agent input part 11. The supplied tablets 13 are dissolved by the processing liquid in the solid processing agent feeding section 11, but the solid processing agent feeding section 11 → circulation pump 5 → processing section 2 →
Dissolution is promoted by the processing solution circulating from the communication window to the solid processing agent feeding section 11. On the other hand, the supplementary water supply means that received the signal
Replenishing water 18 is replenished in the solid processing agent feeding part 11 by a metering pump 19. On the other hand, the detected light-sensitive material is sequentially conveyed by the roller conveying means in the color developing tank 1A, the bleach-fixing tank 1B, and the stabilizing tanks 1C, 1D and 1E (the automatic developing machine A in FIG. 1).
reference). The color developing tank 1A, the bleach-fixing tank 1B, and the stabilizing tanks 1C, 1D, and 1E, which are processing tanks, respectively, may be provided with the processing agent supply means 17, and may be supplied simultaneously.
Further, the timings supplied by the respective supply means may be different from each other, and further, the predetermined area for controlling the processing agent supply means by the processing agent supply control means 9 has a predetermined area. , 1C, 1D, 1E may be the same, but it goes without saying that they may be different from each other.

Not only in this example but also in the example described below,
In the bleach-fixing tank 1B and the stabilizing tanks 1C, 1D, 1E,
Since it has the same structure as the color developing tank 1A, the processing tank 1 will be described below.
In the following description, the color developing tank 1A and the bleach-fixing tank 1
B, stabilization tanks 1C, 1D, and 1E are all referred to here,
In the drawing, the same reference numerals as those in FIG. 2 having the same functions as those in FIG. 2 are omitted, and the description thereof is omitted here. Further, in order to make the configuration easy to understand, a conveying means for conveying the photosensitive material, etc. Is omitted. Although the filtering means has been described as a preferable example in the present embodiment, the effect of the present invention can be sufficiently achieved without the filtering means in the present invention.

As described above, according to the present invention, the replenishing tank which has been conventionally required is not required, and it is not necessary to secure the space for the replenishing tank, so that the automatic processor can be made compact and the solid processing agent can be used in the processing tank. Since the liquid is supplied, there is no need for liquid preparation work, there is no liquid scattering during liquid preparation, and no adherence or contamination to human bodies, clothes, or peripheral devices, and handling is easy.
It has an excellent effect that the replenishment accuracy to the treatment liquid is increased and the treatment components to be replenished are not deteriorated and have stable treatment characteristics.

Next, as another example of the present invention, FIG.
FIG. 2 is a schematic view of the color developing tank 1A in the I-I cross section of the automatic developing machine A of FIG. FIG. 4 is a schematic top view showing the automatic developing machine A of FIG. 1 from the top (however, the route is described for the rehydration means for explanation). FIG. 5 is a block diagram relating to the control according to this example. FIG. 6 is a block diagram in which a pre-programmed evaporative replenishment water setting means 23 is added to the control means. 3 and 4, a replenishing water tank 43 for storing replenishing water is shown. Further, in this example, a case where a tablet is used as the solid processing agent 13 will be described.

First, portions in FIGS. 3 and 4 different from those in FIG. 2 will be described. The replenishment water supply means 42 is means for replenishing the treatment agent receiving portion 11 with replenishment water (replenishment water) from a replenishment water tank 43 that stores replenishment water, and is a hot water replenishment device 32 including a pump, a temperature controller, etc. It has 33 and a replenishment pipe 36.
The replenishing water supply means 42 is for compensating the water taken out by the photographic material and the water evaporated from the surface of the tank, while diluting the cumulative suppressing component eluted by the reaction. A replenishment water tank or a replenishment water pump may be provided for each of the treatment tanks 1A, 1B, 1C, 1D, 1E, but the replenishment water to be replenished is the same replenishment water in any tank,
If you use one refill water tank, the machine will be compact,
More preferably, only one replenishing water tank and replenishing water pump are provided in the automatic developing machine, and a solenoid valve is provided in a replenishing water passage (pipe or the like) so that each treatment tank is replenished with a necessary amount when necessary. Alternatively, by adjusting the diameter of the replenishment pipe to adjust the amount of replenishment, only one replenishment tank 43 and one replenishment pump can be provided in the automatic machine, and the size is further reduced. The stabilizing tanks 1C and 1 which are processing tanks, respectively.
Regarding D, by supplying the stabilizing solution overflowing from the stabilizing tanks 1D and 1E, respectively, the replenishing water supply means can be omitted. Further, it is preferable that the replenishing water in the replenishing water tank is temperature-controlled. The water supplied is
Not only general water such as well water and tap water, but also antifungal agents such as isothiazoline-based and chlorine-releasing compounds and some sulphite chelating agents, ammonia and inorganic salts, etc. Known compounds and means can be used as long as they do not affect the above. .

This replenishment water control means controls the replenishment water supply means 42 by means of the evaporation replenishment water replenishment setting means 23 which is preprogrammed according to the environmental temperature and humidity (relative humidity) of the installation location, and / or the processing amount information detecting means. 8 is a control means for controlling the replenishment water supply means 42 according to the processing amount information and the like detected by 8. The replenishment water supply control means is not limited to responding to the processing amount information detected by the processing amount information detecting means 8, but is controlled according to the information that the processing agent has been supplied by the processing agent supplying means 17. Good.

3 and FIG. 2 are the same as those in FIG. 2 except for the above, the functions and the like are the same.
I will explain it. The heater 7 is arranged at the bottom of the processing unit 2 and heats the processing liquid in the processing unit 2. In other words, the heater 7 is suitable for processing the processing liquid in the processing unit 2 and the solid processing agent feeding unit 11. It also has a temperature control function of maintaining the temperature in a different temperature range (for example, 20 to 55 ° C). A circulation pipe 4 and a circulation pump 5 are provided as circulation means in the same manner as in FIG. 2. However, the difference from FIG. 2 is that the direction of circulation of the treatment liquid is opposite, that is, the treatment liquid is treated in the treatment section 2 The circulation pump 5 is circulated in the order of the solid processing agent feeding section 11 → the communication window → the processing section 2.

The processing agent supply means 17 supplies the tablet 13 which is the solidified processing agent enclosed in the cartridge 15 to the filtering section (section) 14 in the solid processing agent input section 11 by the pushing claw 18. . 2 differs from that in FIG. 2 in that the cam 19 is actuated by the shaft 1 rotation stop mechanism and the push claw 18 is actuated, and the tablet 13 in standby is supplied to the processing tank 1, and the next tablet 13 is the tablet push spring. Since the spring is urged from the upper side to the lower side by the 21, it quickly enters the standby state. At this time, the treating agent supplying means 17 may be a horizontal type or a pushing-up type from below, and any means may be used as long as it can add the solid treating agent to the treating tank 1.

Next, the operation of the present invention will be described with reference to FIGS. 1, 3, 4, and 5. The processed amount information of the exposed photosensitive material is detected by the processed amount information detecting means 8 at the entrance of the automatic developing machine A. The processing agent supply control means 9 is
When the accumulated area of the photosensitive material to be processed reaches a predetermined area in accordance with the processing amount information detected by the processing amount information detecting means 8, a supply signal is issued to the processing agent supplying means 17. Upon receiving the supply signal, the processing agent supplying means 17 causes the extruding member 10 to tablet 13
And press the tablet 13 into the filtering section 14 in the solid processing agent feeding section 11.
Supply to. The supplied tablets 13 are solid processing agent input section 11
It is dissolved by the processing liquid in the inside, but by the circulation means, the processing section 2 → the circulation pump 5 → the solid processing agent feeding section 11 → the communication window →
Dissolution is promoted by the processing solution circulating with the processing section 2. On the other hand, when the cumulative area of the photosensitive material to be processed reaches a predetermined area according to the processing amount information detected by the processing amount information detecting means 8, the supplementary water supplying control means 42 (warm water A rehydration signal is sent to the replenishing device 32 and the solenoid valve 33). Upon receiving the replenishment water signal, the replenishment water supply means 42 controls the hot water replenishment device 32 and the solenoid valve 33 to supply the replenishment water stored in the replenishment water tank 43 to each treatment tank or a required treatment tank by a predetermined amount. Or, replenish the required amount of water. The predetermined area in this case is the same amount as that in the processing agent supply control means 9, but is not limited to this and may be different predetermined areas. On the other hand, the detected light-sensitive material is sequentially conveyed by the roller conveying means in the color developing tank 1A, the bleach-fixing tank 1B, and the stabilizing tanks 1C, 1D and 1E which are processing tanks.

Although the automatic processor including various processing tanks has been described above, the processing tanks include a developing tank for containing a developing solution, a bleaching tank for containing a fixing solution, and a bleach-fixing solution. A bleach-fixing tank, a fixing tank for containing a fixing solution, and a stabilizing tank for containing a stabilizing solution, and at least the accommodating means and / or fixing means, the supplying means, and the control means are respectively described above. An automatic developing machine for a color negative film provided for each processing tank and a developing tank for containing a developing solution as a processing tank, and a fixing tank for containing a fixing solution, and at least the storage means and / or The effect of the present invention was also found in the automatic developing machine for black-and-white silver halide photographic light-sensitive material, in which the fixing means, the supplying means and the controlling means are provided for each of the processing tanks. Example 2 Tables 1 and 2 show the kit forms of conventional treatment agents.
It shows in Table 3.

[0118]

[Table 1]

[0119]

[Table 2] In the table, EDTA / Fe salt represents ethylenediaminetetraacetic acid ferric ammonium, and EDTA-4H represents ethylenediaminetetraacetic acid.

[0120]

[Table 3] The forms of the treating agent of the present invention are shown in Tables 4, 5 and 6.

[0121]

[Table 4]

[0122]

[Table 5] In the table, EDTA-Fe salt represents ethylenediaminetetraacetic acid ferric ammonium salt.

[0123]

[Table 6] Next, the processing agents according to the present invention will be described with reference to Tables 7 and 8.

[0124]

[Table 7]

[0125]

[Table 8] Here, a processing agent for color paper will be described as an example. In the conventional treatment agent, each additive material is concentrated in the liquid part for the purpose of simplifying the dissolving operation at the store where the minilab is installed. In such a case, materials that are stable for a long period are combined into several types of parts. No matter how thick these kits are made, the solubility of the original drug is limited, and water is added in addition to the essential chemical materials. In particular, mixing unnecessary water means carrying water in an extreme way, which increases the burden on transportation costs.

In addition, the treating agent of the present invention is solidified and does not require mixing of water at all, and therefore, it is possible to take a treating agent form of only essential chemical materials. Therefore, Table 1
.About.3 and Tables 4 to 6, the weight of the replenisher for the same processing amount of the light-sensitive material can be reduced to 46% for the color developing replenisher, 23% for the bleach-fixing replenisher and 23% for the super stabilizer.

Next, Table 7 shows the characteristics of the treating agent of the present invention. Generally, the minilab treating agent, the minilab quick treating agent, and the large laboratory treating agent take the part structure as shown in Table 7. .. The conventional processing agent is a minilab quick processing agent that dissolves the processing agent as a replenishing solution and replenishes it according to the processing amount of the photosensitive material. It is getting bigger and bigger. There is a limit to increasing the concentration of the replenisher. There is a limit of about 1.7 times as much as the color developing solution of the tank solution, and about 2.2 times as much as the tank solution of the bleach-fixing solution (which is not shown here, but the solution having a bleaching ability for negative processing is similar). .

When the replenisher is stored at the above concentration, the color developing replenisher causes precipitation of the color developing agent, and the bleach-fixing agent causes precipitation of ferric ethylenediaminetetraacetic acid. In particular, it is easily affected by temperature, causing troubles in the winter when the temperature around the refill tank is 10 ° C or less. In addition, since the kit part is configured in consideration of the storage stability of the liquid kit, depending on the product, the pH may be extremely low or may be extremely high. Therefore, the operator needs to pay attention to the handleability of the kit solution. If the kit solution leaks, gets on your clothes, or gets on your skin, an unexpected accident may occur. That is, leaking a kit solution with a low pH or a kit solution with a high pH and causing it to rust if it comes into contact with a metal part, or if it gets on clothing, that part will be damaged, and if it gets on the skin, that part will fog or eczema. . In addition, the transportation of processing agents is subject to legal restrictions. In other words, it is stipulated by UN (United Nations) rules, etc., and it is necessary to comply with the Ship Safety and Health Law and the Aviation Law. In the case of air transportation, there are some parts that must comply with IATA rules. Items marked with an X in the table for corrosiveness and safety in transportation cannot be transported unless they are filled in a container that has passed the container inspection of the relevant kit.

Further, since the processing agent of the present invention is solidified and does not need to be dissolved as a replenishing solution, it can be directly replenished to the tank solution in accordance with the processing amount of the photosensitive material. Only by increasing the ratio of consumption components,
Since it has an advantageous structure not limited to the solubility, there is no fear of material precipitation problems. Further, since the kit is not a liquid, the weight can be reduced and the burden of transportation cost can be reduced. Furthermore, consideration for corrosiveness and transportation safety is unnecessary. (Example 3) Konica QA Paper Type A5 (Konica
Image-wise exposed to Konica Big Mini Lab B.
M-101 (manufactured by Konica Corp.) was modified into the peel-open system shown in FIG. 17 and further modified so that the treatment steps shown in Table 9 were achieved, and continuous treatment was performed.

[0130]

[Table 9] Stable was a countercurrent system from 3 to 1, and all the overflow liquid of stable-1 was flowed into the bleach-fixing tank. The carryover per 1 m ^{2 of} light-sensitive material is 50 ml / m in all tanks.
^{Was 2} . Evaporation correction is performed for each color development, bleach-fixing, and stability 9.0ml / hr, 7.2ml / hr, 14.1ml / hr every 1 hour during temperature control, and 3.8 for each when temperature control is not performed. m
L / hour, 3.1 ml / hour, and 6.1 ml / hour were integrated, and the temperature control was started at the same time. The tank liquid at the start is Konica Color QA Paper color development starter 82P-1B, (Konica
Konica color QA paper bleach-fix starter manufactured by K.K.
82P-2B (same as above) and Konica Color QA Paper stable starter 82P-3B (same as above). The following operations (A
~ G), treated tablets for color paper were prepared. 1) Tablet operation for color development replenishment for color paper (A) Developing agent CD-3 [4-amino-3-methyl-N-ethyl-N- [β-
(Methanesulfonamide) ethyl] aniline sulfate] 1200
Mill g in a commercial Van Dam mill to an average particle size of 10 μm. This fine powder was granulated in a commercial stirred granulator at room temperature for about 7 minutes by adding 50 ml of water, and then the granulated product was dried in a fluidized bed dryer at 40 ° C. for 2 hours. The water content of the granulated product is almost completely removed. In this way, 150 g of polyethylene glycol 6000 was added to the adjusted granules at 25 ° C and 40
Mix evenly for 10 minutes using a mixer in a room conditioned to below% RH. Next, N-lauroylalanine sodium 4g
Was added and mixed for 3 minutes, and the resulting mixture was compressed into tablets with a tableting machine modified from Tough Pressed Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd., so that the filling amount per tablet was 3.2 g, and 400 Individual tablets A for color development replenishment for color paper were prepared. Operation (B) Disulfoethylhydroxylamine disodium salt 120 g
Is pulverized and granulated in the same manner as in the operation (A). The amount of water added is 6.
After granulating to 0 ml, the granulated product is dried at 50 ° C. for 30 minutes to almost completely remove water from the granulated product. In this way, N-lauroylalanine sodium 4 was added to the prepared granules,
Mix for 3 minutes using a mixer in a room where the temperature is controlled to 40 ° C and 40% RH or less. Next, the mixture thus obtained was compressed into tablets using a tableting machine modified from Tough Pressed Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd., so that the filling amount per tablet was 1.0 g.
0 tablets B for color development replenishment for color paper were prepared. Operation (C) Tinopearl SFP (manufactured by Ciba Geigy) 30.0 g, sodium sulfite 3.7 g, potassium bromide 0.3 g, diethylenetriamine pentaacetic acid 25 g, sodium p-toluenesulfonate 280
After crushing g, 20 g of potassium hydroxide and 10.6 g of mannitol in the same manner as in (A), they are uniformly mixed with a commercially available mixer. Then, in the same manner as in (A), the amount of water added is adjusted to 20 ml and granulation is performed. After the granulation, the granulated product is dried at 60 ° C for 30 minutes to almost completely remove the water content of the granulated product. In this way, 4 g of sodium N-lauroylalanine was added to the prepared granules, and 2
Use a mixer in a room where the temperature is controlled to 5 ° C and 40% RH or less 3
Mix for minutes. Next, the resulting mixture was compressed into tablets using a tableting machine modified from Tough Pressed Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd., so that the filling amount per tablet was 1.0 g.
100 tablets of color development supplement C for color paper were prepared. Operation (D) 350 g of potassium carbonate is pulverized and granulated in the same manner as in the operation (A). The amount of water added is 20 ml, and after granulation, the granules are dried for 30 minutes to remove water almost completely. In this way, polyethylene glycol 6000 was added to the adjusted granules.
Mix 15 g uniformly in a room controlled at 25 ° C. and 40% RH or less for 10 minutes using a mixer. Next, 4 g of sodium N-lauroylalanine was added and mixed for 3 minutes, and then the obtained mixture was manufactured by Kikusui Seisakusho Co., Ltd. Tough Pressed Collect 152.
Using a tablet machine modified from 7HU, the filling amount per tablet is 3.
Tablet compression was performed with 0 g to prepare 110 tablet D agents for color development replenishment for color paper. 2) Bleach-fix fixing replenishing tablet for color paper (E) Diethylenetriamine pentaacetic acid ferric ammonium monohydrate
1250g, ethylenediaminetetraacetic acid 25g, maleic acid 250g,
Pine Flow (Matsuya Chemical Co., Ltd.) 46 g is pulverized, mixed and granulated in the same manner as in the operation (C). The amount of water added was 80 ml, and after granulation,
The granules are dried at 60 ° C. for 2 hours to almost completely remove water. Thus, 15 g of N-lauroyl sarcosine sodium is added to the prepared granulated product, and mixed for 3 minutes by using a mixer in a room whose humidity is controlled to 25 ° C. and 40% RH or less. Next, the resulting mixture was compressed into tablets with a tableting machine modified from Tough Pressto Correct 1527HU manufactured by Kikusui Seisakusho Co., Ltd. with a filling amount of 8.6 g per tablet, and bleach-fixing replenishment for 170 color papers. Tablet A for tablets was prepared. Operation (F) Ammonium thiosulfate 1640 g, sodium sulfite 750 g,
40 g of potassium bromide and 50 g of p-toluenesulfinic acid are pulverized, mixed and granulated in the same manner as in the operation (C). The amount of water sprayed is 10
After granulating to 0 ml, the granulated product is dried at 60 ° C. for 120 minutes to almost completely remove water from the granulated product. In this way, 20 g of sodium N-lauroylsarcosine was added to the adjusted granules,
Use a mixer in a room where the temperature is controlled to 5 ° C and 40% RH or less 3
Mix for minutes. Next, the resulting mixture was compressed into tablets with a tableting machine modified from Tough Pressto Correct 1527HU manufactured by Kikusui Seisakusho Co., Ltd. with a filling amount of 13.4 g per tablet, and bleach-fixing replenishment for 180 color papers. Tablet B formulation was prepared. 3) Tablet for stable replenishment for color paper (G) Sodium carbonate monohydrate 10g, 1-hydroxyethane-1,1-
Disodium diphosphonate 200g, Chinopearl SFP150
g, sodium sulfite 300g, zinc sulfate heptahydrate 20g, ethylenediamine tetraacetic acid disodium 150g, ammonium sulfate
200 g, 10 g of o-phenylphenol and 25 g of pine flow are pulverized, mixed and granulated in the same manner as in the operation (C). How much water is added
After granulating to 60 ml, the granulated product is dried at 70 ° C. for 60 minutes to almost completely remove the water content of the granulated product. In this way, 10 g of sodium N-lauroylsarcosine was added to the adjusted granules,
Use a mixer in a room where the temperature is controlled to 5 ° C and 40% RH or less 3
Mix for minutes. Next, the obtained mixture was compressed into tablets using a tableting machine modified from Tough Pressed Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd. so that the filling amount per tablet was 3.1 g.
We made 360 stable refill tablets for color paper.

As for the above-mentioned tablets for color development replenishment, one tablet for each of agents A, B, C and D, for a total of four tablets, is prepared.
As a separate package, a continuous 20-minute package was packaged by a four-sided sealing method using a peel open packaging material. Regarding the bleach-fixing replenishing tablet, 1 tablet of the agent A and 2 tablets of the agent B were packaged in a total of 3 tablets for 1 minute each, and a continuous 20-minute package was packaged in the same manner as the tablet for replenishing color development.

Further, for tablets for stable replenishment, 1 for each
Each tablet was made into one packet and packaged in the same manner as above. For the replenishment water, calculate the area of the processed photosensitive material
When the temperature reached the maximum, the bellows pump was used to set the amount of replenishment water supplied once to 10 ml, and the replenishment frequency was set to 5 times. Also,
As supplementary water, 0.3 g / l of sodium ethylenediaminetetraacetate was added.

The peel-open packaging material was prepared by using Tocello CMPSO11C as a sealant film and laminating the unstretched polypropylene film / stretched polypropylene film on the unstretched polypropylene film side. The peel-open film thus prepared and the unstretched polypropylene / stretched polypropylene film were heat-sealed, and the tablets were packaged. In addition, as a comparative example, the present tablet and replenishing water corresponding thereto were placed in a replenishing tank and 10 liters of replenishing solution was prepared and used. However, the evaporation correction in the comparison process was performed with the replenisher. The treatment was carried out with 5 m ^{2 of} color paper per day until the overflow amount became twice as much as the tank solution, and then the number of days until the sulfurization in the bleach-fixing tank was observed, and the wedge-exposed sample was developed and the blue The maximum reflection density was measured. However,
The color developing agent in the color developing agent, when the replenishment amount is 50 ml / m ² ,
1.2 times 25 ml / m ² was changed to 1.45 times and 150 ml / m ² was changed to 0.9 times to correct the consumption. The amount of maleic acid in the bleach-fixing solution was increased by the amount corresponding to the increase in pH due to the incorporation of the color developing solution when the replenishment rate was lowered. Table 10 shows a comparative example of each method.

[0134]

[Table 10] Further, the replenishing amount of the replenishing solution and the renewal rate were changed, and continuous processing was performed. The solid processing agent charging method of the present invention was compared with the conventional replenishing solution preparing method, and the concentration of the bleach-fixing solution was measured. The concentration rate is measured by atomic absorption by measuring the concentration of iron ions in the tank liquid,
I asked. Further, it was dissolved in a color developer to observe the dissolved state when a replenisher was prepared.

[0135]

[Table 11] As is clear from Table 11 above, in the conventional replenisher preparation means, if the replenisher is made low, the replenisher must be thickened, and when the replenisher is prepared, it is not completely dissolved and insoluble matter remains. Further, it can be seen that when the replenishment is low, the replenisher is also oxidized and deteriorated, so that the densities cannot be obtained sufficiently by measuring the photographic density.

On the other hand, in the direct charging method of the present invention, since no replenisher is prepared, neither dissolution nor deterioration occurs. Furthermore, in the case of bleach-fixing solution, the replenisher for low replenishment should be pH
It was found that the sulphur is low and the storage stability is poor, and it sulfides in a few weeks. However, according to the method of the present invention, since it is not necessary to prepare a replenishing solution, sulfuration of the bleach-fixing solution does not occur at all. In addition, when the concentration of the bleach-fix solution is measured, the current replenisher method causes a large concentration in the low replenishment area, and especially in the area where the replenishment amount is smaller than the evaporation amount, the evaporation rate with the replenishment solution is higher, and the concentration rate is further increased. Become. However, in the case of the present invention, since evaporation correction can be separately performed, concentration is not carried out at all, and it can be seen that it is really good. Figure 9 shows the relationship between the amount of replenishment and the concentration ratio.
FIG. 9 is a characteristic diagram comparing a conventional technique and the present invention. (Example 4) Experiment No. 3 of Example 3 was used. In the above, the same experiment as in Example 3 was conducted by changing the timing of replenishing replenishing water as shown in Table 12, and the maximum concentration of blue in the processed light-sensitive material was measured and summarized in Table 12.

[0137]

[Table 12] (Example 5) As a mildewproof means in the replenishment tank of the hot water replenishing device 32 of FIG. 4 (1) 0.5 g / l of ethylenediaminetetraacetic acid was added (2) 0.1 g of 1,2-benzisothiazolin-3-one
/ l addition (3) 5-chloro-2-methyl-4-isothiazoline-
0.1 g / l of 3-one added (4) Diaion SK1B (strongly acidic cation exchange resin, manufactured by Mitsubishi Kasei) and Diaion PA406 (OH type strongly basic anion exchange resin, manufactured by Mitsubishi Kasei) in a volume ratio of 1 Mixed at 1. Uses ion-exchanged water (5) Uses UV irradiation device (Kindai Bio Ken) (6) Biosure SGD (Kinki Pipe Giken) 1g /
1 addition (7) The same experiment as in Example 3 was carried out without using the antifungal means. The results were exactly the same except for (7). Furthermore, the state in the rehydration tank was visually observed. The results were good except for (7), and in (7), scum was generated on the surface and the wall. (7) is uneven development,
This is because desilvering unevenness and stains were severe, and the suspended matter in the replenishing water tank entered each processing tank and adhered to the photosensitive material. (Example 6) Konica QA Paper Type-5 (Konica
After imagewise exposing (manufactured by Konica Corp.), a modified NPS-808 machine (manufactured by Konica Corp.) having the configuration shown in FIG. 1 was processed according to the following processing steps. However, the replenishment water in the replenishment tank was deionized.

Processing step Processing time Processing temperature Tank capacity Color development 22 seconds 38.0 ° C 12l Bleach fixing 22 seconds 37.5 ° C 12l Stable -1 22 seconds 35 ° C 12l Stable-2 22 seconds 35 ° C 12l Stable -3 22 seconds 35 ° C 12l Dry Drying 50 seconds 55 ° C Stability is a countercurrent system from 3 to 1, and all the overflow liquid of Stable-1 was made to flow into the bleach-fixing tank. The carryover of the light-sensitive material per 1 m ² of light-sensitive material is 45 ml from the color developing tank to the bleach-fixing tank and 50 m from the bleach-fixing tank to the stabilizing tank.
l, stable-1 to 2, 2 to 3 and 3 to dry was 40 ml. The opening area of each of the color developing tank, the bleach-fixing tank and the stabilizing tank was 4.5 cm ² per liter of the processing solution. The outside air of the automatic processing machine is 27 ℃, 60
% RH, and the replenishing water was replenished when the amount of evaporation reached 100 ml. The means for calculating the replenishment water is disclosed in JP-A-3-2800.
The formula (1) of Japanese Patent Laid-Open No. 42 was used. The processed photosensitive material is 1
It was treated at 2.0 m ² per day and continuously for 2 months. The composition of the treatment liquid is shown below. (Color developer) Potassium bromide 0.02g Potassium chloride 3.2g Potassium carbonate 30g Potassium sulfite 0.2g Diethylenetriamine sodium pentaacetate 2g Sodium nitrilotrimethylenephosphonate 2g Tinopearl SFP 2g Disodium-N, N-bis (sulfonate ethyl) hydroxylamine 5 g 4-Amino-3-methyl-N-ethyl N- [β- (methanesulfonamido) ethyl] aniline sulfate 7 g (CD-3) Water was added to 1 l and the pH was adjusted to 10.10. (Bleach-fixing solution) Ammonium ferric ammonium diethylenetriaminepentaacetate 100 g Diethylenetriaminepentaacetic acid 2 g Ammonium thiosulfate 120 g Ammonium sulfite 40 g Sulfinic acid 5 g Ammonium bromide 10 g Water was added to 1 l and the pH was adjusted to 7.0. (Stabilizer) Water 800g 1,2-Benzisothiazolin-3-one 0.1g 1-Hydroxyethylidene-1,1-diphosphonic acid 5.0g Ethylenediaminetetraacetic acid 1.0g Chinopearl SFP (Ciba-Geigy) 2.0g Ammonium sulfate 2.5g Zinc chloride 1.0 g Magnesium chloride 0.5 g o-Phenylphenol 1.0 g Sodium sulfite 2.0 g Water was added to make 1 liter, and the pH was adjusted to 8.0 with 50% sulfuric acid or 25% aqueous ammonia. The processing tablets used were those prepared in Example 2.

Next, the above tablets were sealed one by one using a laminated polymer resin film made of PET / polyvinyl alcohol / ethylene copolymer / polyethylene, and introduced using the supply device shown in FIG. The above tablets are added one by one when color paper is processed to 1 m ² , and at the same time, 76 ml of replenishing water from the replenishing water tank to the color developing tank and to the bleach-fixing tank.
42 ml and 247 ml were supplied to the stabilizing tank.
In this case, the amount of replenishment water per time was set to 10 ml. As a comparison, the same running test was conducted on the color developing tank, the bleach-fixing tank, and the stabilizing tank with water up to the overflow port once every morning and evening. as a result,
In the case of the present invention, the sensitivity variation was within ± 1%, but when water was replenished to the overflow port every morning and evening, ±
It was 4%, and it was found that the photographic performance was stable when the evaporative water replenishing means of the present invention was adopted. (Example 7) A treated tablet for color paper was prepared according to the following procedure. 1) Tablet operation for color development replenishment for color paper (A) Developing agent CD-3 [4-amino-3-methyl-N-ethyl-N- [β-
(Methanesulfonamide) ethyl] aniline sulfate] 1200
Mill g in a commercial Van Dam mill to an average particle size of 10 μm. This fine powder was granulated in a commercial stirred granulator at room temperature for about 7 minutes by adding 50 ml of water, and then the granulated product was dried in a fluidized bed dryer at 40 ° C. for 2 hours. The water content of the granulated product is almost completely removed. In this way, 150 g of polyethylene glycol 6000 was added to the adjusted granules at 25 ° C and 40
Mix evenly for 10 minutes using a mixer in a room conditioned to below% RH. Next, N-lauroylalanine sodium 4g
Was added and mixed for 3 minutes, and the resulting mixture was compressed into tablets with a tableting machine modified from Tough Pressed Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd., so that the filling amount per tablet was 3.2 g, and 400 Individual tablets A for color development replenishment for color paper were prepared. Operation (B) Disulfoethylhydroxylamine disodium salt 120 g
Is pulverized and granulated in the same manner as in the operation (A). The amount of water added is 6.
After granulating to 0 ml, the granulated product is dried at 50 ° C. for 30 minutes to almost completely remove water from the granulated product. In this way, 4 g of sodium N-lauroylalanine was added to the prepared granules,
Mix for 3 minutes using a mixer in a room where the temperature is controlled to 40 ° C and 40% RH or less. Next, the mixture thus obtained was compressed into tablets using a tableting machine modified from Tough Pressed Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd., so that the filling amount per tablet was 1.0 g.
0 tablets B for color development replenishment for color paper were prepared. Operation (C) Tinopearl SFP (manufactured by Ciba Geigy) 30.0 g, sodium sulfite 3.7 g, potassium bromide 0.3 g, diethylenetriamine pentaacetic acid 25 g, sodium p-toluenesulfonate 280
After crushing g, 20 g of potassium hydroxide and 10.6 g of mannitol in the same manner as in (A), they are uniformly mixed with a commercially available mixer. Then, in the same manner as in (A), the amount of water added is adjusted to 20 ml and granulation is performed. After the granulation, the granulated product is dried at 60 ° C for 30 minutes to almost completely remove the water content of the granulated product. In this way, 4 g of sodium N-lauroylalanine was added to the prepared granules, and 2
Use a mixer in a room where the temperature is controlled to 5 ° C and 40% RH or less 3
Mix for minutes. Next, the resulting mixture was compressed into tablets using a tableting machine modified from Tough Pressed Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd., so that the filling amount per tablet was 1.0 g.
100 tablets of color development supplement C for color paper were prepared. Operation (D) 350 g of potassium carbonate is pulverized and granulated in the same manner as in the operation (A). The amount of water added is 20 ml, and after granulation, the granules are dried for 30 minutes to remove water almost completely. In this way, polyethylene glycol 6000 was added to the adjusted granules.
Mix 15 g uniformly in a room controlled at 25 ° C. and 40% RH or less for 10 minutes using a mixer. Next, 4 g of sodium N-lauroylalanine was added and mixed for 3 minutes, and then the obtained mixture was manufactured by Kikusui Seisakusho Co., Ltd. Tough Pressed Collect 152.
Using a tableting machine modified from 7HU, compression tableting was performed so as to obtain the filling amount shown in Table 1 to prepare 110 color development replenishing tablet D agents for color paper. 2) Bleach fixing replenishment tablet for color paper (E) Ethylenediaminetetraacetic acid ferric ammonium monohydrate 1250
g, ethylenediaminetetraacetic acid 25 g, maleic acid 250 g, pine flow (Matsuya Chemical Co., Ltd.) 46 g, crushed in the same manner as in step (C),
Mix and granulate. The amount of water added is 80 ml, and after granulation, 60 ℃
The granules are dried for 2 hours to almost completely remove the water content.
Thus, 15 g of N-lauroyl sarcosine sodium is added to the prepared granulated product, and mixed for 3 minutes by using a mixer in a room whose humidity is controlled to 25 ° C. and 40% RH or less. Next, the obtained mixture was tough pressed collect 1 manufactured by Kikusui Seisakusho KK
A tableting machine modified from 527HU was used to perform compression tableting with the filling amount per tablet being 8.6 g, to prepare 170 bleach-fixing replenishing tablet A agents for color paper. Operation (F) Ammonium thiosulfate 1640 g, sodium sulfite 750 g,
40 g of potassium bromide and 50 g of p-toluenesulfinic acid are pulverized, mixed and granulated in the same manner as in the operation (C). The amount of water sprayed is 10
After granulating to 0 ml, the granulated product is dried at 60 ° C. for 120 minutes to almost completely remove water from the granulated product. In this way, 20 g of sodium N-lauroylsarcosine was added to the adjusted granules,
Use a mixer in a room where the temperature is controlled to 5 ° C and 40% RH or less 3
Mix for minutes. Next, the resulting mixture was compressed to a filling amount shown in Table 1 by a tableting machine which was modified from Tough Pressto Correct 1527HU manufactured by Kikusui Seisakusho Co., Ltd., and bleach-fixing replenishing tablet B agent for color paper. It was created. 3) Tablet for stable replenishment for color paper (G) Sodium carbonate monohydrate 10g, 1-hydroxyethane-1,1-
Disodium diphosphonate 200g, Chinopearl SFP150
g, sodium sulfite 300g, zinc sulfate heptahydrate 20g, ethylenediamine tetraacetic acid disodium 150g, ammonium sulfate
200 g, 10 g of o-phenylphenol and 25 g of pine flow are pulverized, mixed and granulated in the same manner as in the operation (C). How much water is added
After granulating to 60 ml, the granulated product is dried at 70 ° C. for 60 minutes to almost completely remove the water content of the granulated product. In this way, 10 g of sodium N-lauroylsarcosine was added to the adjusted granules,
Use a mixer in a room where the temperature is controlled to 5 ° C and 40% RH or less 3
Mix for minutes. Next, the mixture thus obtained was compressed into tablets using a tableting machine modified from Tough Pressed Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd. so that the filling amount was as shown in Table 1 to prepare stable supplement tablets for color paper. . Each of the above-mentioned supplementary tablets for color paper is four-sided sealed using a laminated polymer resin film made of PET / polyvinyl alcohol / ethylene copolymer / polyethylene so that the amounts shown in Tables 7 and 8 are obtained, Further, each part of each replenisher was tableted, the total amount was set to the amount shown in Table 2 so that the component ratio was the same as one tablet, and four-way sealing was performed by the same means as above. It should be noted that each cartridge has a 20-minute package.

Next, Konica Color QA Paper Type 5
After imagewise exposing (manufactured by Konica Corp.), N shown in FIG.
It was processed by a modified PS-808 according to the following processing steps. However, as the replenishing water in the replenishing tank, benzisothiazoline was added in an amount of 0.1 g per liter of the replenishing water.

Processing step Processing time Processing temperature Tank capacity Color development 22 seconds 38.0 ° C 12l Bleach fixing 22 seconds 37.5 ° C 12l Stable -1 22 seconds 35 ° C 12l Stable-2 22 seconds 35 ° C 12l Stable -3 22 seconds 35 ° C 12l Dry Drying 50 seconds 55 ° C Stability is a countercurrent system from 3 to 1, and all the overflow liquid of Stable-1 was made to flow into the bleach-fixing tank. The carryover of the light-sensitive material per 1 m ² of light-sensitive material is 45 ml from the color developing tank to the bleach-fixing tank and 50 m from the bleach-fixing tank to the stabilizing tank.
l, stable-1 to 2, 2 to 3 and 3 to dry was 40 ml. The opening area of each of the color developing tank, the bleach-fixing tank and the stabilizing tank was 4.5 cm ² per liter of the processing solution. The composition of the treatment liquid is shown below. (Color developer) Potassium bromide 0.02g Potassium chloride 3.2g Potassium carbonate 30g Potassium sulfite 0.2g Diethylenetriamine sodium pentaacetate 2g Sodium nitrilotrimethylenephosphonate 2g Tinopearl SFP 2g Disodium-N, N-bis (sulfonate ethyl) hydroxylamine 5 g 4-Amino-3-methyl-N-ethyl N- [β- (methanesulfonamido) ethyl] aniline sulfate 7 g (CD-3) Water was added to 1 l and the pH was adjusted to 10.10. (Bleach-fixing solution) Ammonium ferric ammonium diethylenetriaminepentaacetate 100 g Diethylenetriaminepentaacetic acid 2 g Ammonium thiosulfate 120 g Ammonium sulfite 40 g Sulfinic acid 5 g Ammonium bromide 10 g Water was added to 1 l and the pH was adjusted to 7.0. (Stabilizer) Water 800g 1,2-Benzisothiazolin-3-one 0.1g 1-Hydroxyethylidene-1,1-diphosphonic acid 5.0g Ethylenediaminetetraacetic acid 1.0g Chinopearl SFP (Ciba-Geigy) 2.0g Ammonium sulfate 2.5g Zinc chloride 1.0 g Magnesium chloride 0.5g o-Phenylphenol 1.0g Sodium sulfite 2.0g Water was added to make 1 liter, and pH was adjusted to 8.0 with 50% sulfuric acid or 25% aqueous ammonia.

The running experiment was carried out on 50 prints of 24EXP color film per hour for 3 hours continuously.
750 sheets) were processed and the tablet solubility, photographic performance, handleability, etc. at that time were evaluated. The amount of tablets and the amount of supplementary water are shown in Table 13.

[0143]

[Table 13] Color paper is 1 when tablets and replenishment water enter
When processed with m ² , the color developing replenishing tablet 7.85g, replenishing water 80ml, the bleach-fix replenisher tablet 39.7g, replenishing water 2
Refilling water (250 ml) is replenished with 00 ml and stable replenishing tablets (2.6 g). Addition time (Table 1
When 4) is replaced and the amount of rehydration water reaches the above-mentioned tablet amount, 80 ml and 2 respectively
00 ml and 250 ml were supplied so that the amount of replenishing water per time was 10 ml.

[0144]

[Table 14] As a result, in terms of workability of replacing the tablet cartridge, adhesion of the tablet to the packaging material, solubility of the tablet, and processing stability, when the entire replenisher is solidified and separated from the replenishing water, the replenisher is replenished.
It was also found that 0.5g to 30g was particularly good. Example 8 A fixing tablet was prepared according to the following procedure.
2500 g ammonium thiosulfate, 150 g sodium sulfite,
150 g of potassium carbonate and 20 g of ethylenediaminetetraacetic acid disodium salt are crushed and granulated. The amount of water sprayed is 30 ml,
After granulation, it is dried at 60 ° C for 60 minutes. Then granulate in vacuum
The granulated product is dried at 40 ° C. for 8 hours to almost completely remove water.

The granules grown by the above operation are treated at 25 ° C. and 40% RH.
Mix evenly in a conditioned room for 10 minutes using a mixer. Next, the mixture was compressed into tablets using a tableting machine modified from Tough Press To Correct 1527HU manufactured by Kikusui Seisakusho, with the filling amount per tablet being 9.0 g, to prepare 200 replenishing fixing tablets for color negative. Next, fixer of the following prescription
It was made for 10 liters.

[Fixing Solution Composition] (1 L Formulation) Ammonium thiosulfate 250 g Sodium sulfite 15 g Potassium carbonate 15 g EDTA-2Na 2 g The above fixing solution is a dissolution test unit (A) shown in FIG. 7 below.
Magnet pump M made of Iwaki that fills the processing tank inside
The above tablets were charged into the auxiliary tank at a rate of one tablet per minute while circulating with D-5. Also, tap water at the same time
20 ml was added to the treatment tank. The temperature of the treatment liquid in the treatment tank and the auxiliary tank was changed by the temperature control unit as shown in the table below, and the remaining state of the tablets in the auxiliary tank was observed when 100 tablets were continuously added.

For comparison, the dissolution test unit (B) shown in FIG. 8 was used, and the same tablet and 20 ml of dissolution water were simultaneously added to the replenisher preparation unit every minute, and the mixture was stirred for 30 seconds by the stirring unit. Added to auxiliary tank. The liquid temperature of the dissolved water (tap water) was 25 ° C.

[0148]

[Table 15] This experiment was a high-speed dissolution experiment assuming replenishment equivalent to 60 lines per hour in an automatic processor, and evaluation was performed using a fixing agent having the highest dissolution frequency. As is clear from Table 15, in the method of directly adding the processing agent to the processing solution, which is the dissolution means of the present invention, the temperature of the processing tank can be dissolved at 25 ° C or higher without leaving any insoluble matter, and depending on the temperature, dissolution You can control the speed. A small amount of insoluble matter remained at 20 ° C, but there was almost no problem in practical use. Further, as in the case of the unit (B) shown in FIG. 8, the method of once dissolving with the replenishing solution forming filter does not dissolve within the specified time, so that all of them are clogged in the filter and cannot operate. Further, assuming that tablets were charged before the temperature control was completed by the heater, the charging was started 10 minutes before the temperature control was completed, but there was no problem in dissolution in the unit (A). (Example 9) After Konica Color Super DD-100 film was imagewise exposed, the color negative film processor CL-KP-50QA was modified into a system in which a peel-open packaging material can be used and subjected to continuous processing. Show this process step
Shown in 16.

[0149]

[Table 16] Fixing was a countercurrent system from 2 to 1, stability was from 3 to 2, 2 to 1, and the bleaching tank was aerated with an air pump. Evaporation correction is color development, bleaching,
Fixing-1, Fixing-2, Stable-1, Stable-2, Stable-3 tanks with 10ml, 6.5ml, 7ml, 7ml, 8.6ml and 8.6m per hour respectively
Evaporation correction was performed using a program that rehydrates 9.3 ml of water. In addition, when not in operation, the non-operation time is added up, color development,
Bleaching, fixing-1, fixing-2, stable-1, stable-2, stable-3 with evaporation-corrected water of 7.5 ml, 5 ml and 6 m per hour respectively
A total of 1, 6 ml, 5 ml, 5 ml and 5 ml were replenished with water at the start of operation. The tank solution at the start was prepared by using a replenisher solution of Konica Color Negative Film processing agent CNK-4-52 and a starter. A treated tablet for color negative film was prepared according to the following procedure. 1) Tablet operation for color development replenishment for color negative (1) 150 g of CD-4 [4-amino-3-methyl-N-ethyl-β- (hydroxy) ethylaniline sulfate] as a developing agent is averaged in a commercially available bandam mill. Grind to a particle size of 10 μm. This fine powder was granulated in a commercial stirred granulator at room temperature for about 7 minutes by adding 10 ml of water, and then the granulated material was dried in a fluidized bed dryer at 40 ° C. for 2 hours. The water content of the granulated product is almost completely removed. In this way, N-lauroylalanine sodium 0.3 g and polyethylene glycol 6000 1.9 g were added to the adjusted granules, and the mixture was mixed with a mixer in a room where the temperature was adjusted to 25 ° C and 40% RH or less. Mix evenly for a minute. Next, the mixture is toughly pressed collect 1527H manufactured by Kikusui Seisakusho KK
A tableting machine modified from U was used to perform compression tableting with the filling amount per tablet being 1.1 g, to prepare 126 color developing agent replenishing tablets A for color negative. Operation (2) 69.4 g of hydroxylamine sulfate and 4 g of pine flow (manufactured by Matsutani Chemical Co., Ltd.) were pulverized in the same manner as in operation (1), and then mixed and granulated. The amount of water added is 3.5 ml, and after granulation, it is dried at 60 ° C. for 30 minutes to almost completely remove the water content of the granulated product. In this way, 0.3 g of sodium N-lauroylalanine is added to the adjusted granulated product, and mixed for 3 minutes using a mixer in a room where the humidity is adjusted to 25 ° C. and 40% RH or less. Further, by the same means as in the operation (1), compression tableting was carried out with a tableting machine at a filling amount of 0.56 g per tablet, to prepare 120 color developing replenishing tablet B agents for color negative. Operation (3) 1-hydroxyethane-1,1-diphosphonate disodium 15
g, potassium sulphite 72.8g, potassium carbonate 375g, sodium hydrogen carbonate 3g, sodium bromide 3.7g and mannite 22g are crushed and mixed in the same manner as in step (1), and the amount of water added is 40 ml for granulation. . After the granulation, the granulated product is dried at 70 ° C. for 60 minutes to almost completely remove the water content of the granulated product. In this way, 2 g of sodium N-lauroylalanine was added to the prepared granulated product, and the mixture was mixed for 3 minutes using a mixer in a room where the humidity was adjusted to 25 ° C. and 40% RH or less. Further, by the same method as in the operation (1), compression tableting was carried out with a tableting machine at a filling amount of 3.9 g per tablet to prepare 120 color developing replenishing tablet C agents for color negative. 2) Bleach replenishment tablet operation for color negative (4) 1,3-Propanediamine tetraacetic acid ferric ammonium monohydrate
175 g, 1,3-propanediamine tetraacetic acid 2 g, and Pine Flow (Matsuya Chemical Co., Ltd.) 17 g were pulverized and mixed in the same manner as in the operation (1), and the amount of water added was 8 ml for granulation. After the granulation, the granulated product is dried at 60 ° C for 30 minutes to almost completely remove the water content of the granulated product. Operation (5) 133g succinic acid, 200g ammonium bromide and pine flow 1
0.2 g is pulverized, mixed and granulated in the same manner as in the operation (1). The amount of water added was 17 ml, and after granulation, the granules were dried for 60 minutes at 70 ° C to almost completely remove water. Operation (6) Grind, mix and granulate 66.7 g of potassium sulfate, 60 g of potassium hydrogen carbonate and 8 g of mannite in the same manner as in operation (1). The amount of water added is 13 ml, and after granulation, the granules are dried at 60 ° C for 60 minutes to almost completely remove water. Operation (7) The granules prepared in the above operations (4)-(6) are at 25 ° C and 40%.
Mix evenly for 10 minutes using a mixer in a room whose humidity is adjusted to below RH. Next, 6 g of sodium N-lauroyl sarcosine is added to this mixed granulated product, and the mixture is mixed for 3 minutes. Next, the mixture is toughly pressed collect 1527H manufactured by Kikusui Seisakusho KK
A tableting machine modified from U was used to perform compression tableting at a filling amount of 6.5 g per tablet to prepare 80 bleaching replenishing tablets for color negative. 3) Fixing replenishment tablet operation for color negative (8) Ammonium thiosulfate 2500 g, sodium sulfite 150 g,
Operate 150g of potassium carbonate, 20g of ethylenediamine tetraacetic acid disodium salt and 65g of Pine Flow (Matsuya Chemical) (1)
Grind, mix and granulate as in. The amount of water added was 50 ml, and after granulation, the granules were dried for 120 minutes to almost completely remove water. Operation (9) The granules prepared in the above operation (8) and 13 g of sodium N-lauroylsarcosine are mixed for 3 minutes using a mixer in a room where the humidity is adjusted to 25 ° C and 40% RH or less. Next, the mixture was compressed into tablets with a tableting machine modified from Tough Pressed Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd., so that the filling amount per tablet was 9.3 g, and 280 fixing fixing tablets for color negative were prepared. . 4) Tablet operation for stable replenishment for color negative (10) 150 g of m-hydroxybenzaldehyde, 20 g of sodium lauryl sulfate, 60 g of disodium ethylenediamine tetraacetate,
65 g of lithium hydroxide monohydrate and 10 g of pine flow are pulverized, mixed and granulated in the same manner as in the operation (1). The amount of water added is 10
After the granulation, the granulated product is dried at 50 ° C. for 2 hours to almost completely remove the water content of the granulated product. Operation (11) Each tablet of the granules prepared in the above operation (10) was adjusted in a room where the humidity was adjusted to 25 ° C and 40% RH or less, using a tablet press modified from Tough Pressed Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd. The tablet was compressed and compressed to 0.48 g to prepare 280 stable supplement tablets for color negative.

Next, the above-mentioned tablets were used for color development replenishment tablets, 2 tablets, 1 tablet and 1 tablet each for A, B and C, 2 tablets for bleaching replenishment tablet, 3 tablets for fixing replenishment tablet,
As for tablets for stable replenishment, one tablet was made into one packet, and continuous 20-minute packets were each packaged by a four-side sealing method using a peel-open packaging material. The same peel-open packaging material as that used in Example 3 was used. Further, the timing of replenishing the tablets and makeup water was as shown in Table 17 below. The processing was carried out so that the overflow from the color developing tank was 5% of the tank solution per day.

[0151]

[Table 17] The water was replenished once so that the amount of replenished water was 20 ml.

As a comparative example, the tablets and makeup water were
It was dissolved in a replenishment tank for 10 l and replenished from the replenishment tank.
At this time, replenishment was carried out so that the amount was the same as in the case of the tablets. The evaporation correction was performed every morning up to the overflow port. The photographic densities of the highest density part two months after the start of processing were compared. The results are shown in Table 18.

[0153]

[Table 18] As is clear from Table 18 above, until such processing, in the comparative conventional method, deterioration of the color developing solution occurred and the photographic density was lowered, but in comparison with the method of the present invention, there was no change. I understand. Also, in the method of the present invention, the following liquid was used for one packet instead of the stable supplement tablet, and the same result was obtained.

Diethylene glycol 2.9 g m-Hydroxybenzaldehyde 0.65 g Emulgen 810 (Kao Corporation) 0.2 g (Example 10) Next, regarding the relationship between the continuous state of the treatment and the dissolution state of the solid treatment agent, supply of supplementary water was conducted. An example of control will be described. The processing amount information is information that indirectly detects the situation where the processing agent component in the processing liquid decreases according to the processing amount as described above. Therefore, when the treatment is continuously performed and the treatment agent component in the treatment liquid in the treatment tank sharply decreases, when the supplement of the treatment agent component due to dissolution of the replenishing treatment agent may not be completed in time. Is only information on the amount of treatment, and when supplementary water is supplied, the supplementary water precedes the supplementation of the above treatment agent components, so the supplemental water temporarily becomes excessive and the liquid level in the treatment tank is maintained by the overflow method. In the case of the method described above, a phenomenon occurs in which the treating agent component is diluted with the replenishing water, overflows and is discarded, and further reduction of the treating agent component is induced, which is not preferable. In consideration of such a situation, in this embodiment, the supply of the replenishing water is controlled by the control means that controls the operation in consideration of the dissolution time of the added processing agent or the dissolution and dispersion time of the input processing agent. The control prevents the replenishment water from being supplied one after another while the treatment agent is not dissolved or dissolved and dispersed.

FIG. 6 is a block diagram of the above embodiment. The processing amount information is obtained by the detection means 8, enters the processing agent supply control means 9 and the supplementary water supply control means 9-b, and regarding the processing agent supply control means 9 and the supplemental water supply control means 9-b,
The replenishment water supply means 42 is referred to with reference to the data in Table 9-c regarding the treatment agent dissolution time or the treatment agent dissolution and dispersion time.
Is controlled. As described above, in the case where the treatment agent component of the treatment liquid in the treatment tank sharply decreases by the continuous treatment, the supply of makeup water is performed after the treatment agent is dissolved or dissolved and dispersed.

Next, one comparative example and another embodiment of the present invention will be described. FIG. 11 shows a supply device of a comparative example. Figure
10 shows an example of a one-part agent packaged with two or more components of the present invention, FIG. 10 (A) is a sectional view of a powdery processing agent supply device, and FIG. 14 (B) is a perspective view of the package. . The supply device 50 is a hopper or a package for storing the powdery treatment agent.
51, a metering hole 53 for metering the powdery treatment agent, and a rotary drum 52 for metering a fixed amount. The rotary drum 52 has a moisture-proof function by shifting the positions of the measuring hole 53 and the discharging portion 56. The package 51 was unsealed and loaded on top of the feeder. A certain amount of powdered chemical is measured in the measuring hole 53, and the drum 52 is rotated by the command of the processing amount detecting means of the photosensitive material, and the discharging portion 56.
When it is in a communication state with, it stops and passes through the discharge part 56, and a fixed amount of powdery chemical is supplied to the constant temperature part (filter tank) of the automatic developing machine. After the supply is completed, when the drum 52 rotates and the measuring hole 53 and the supply unit 57 communicate with each other, the drum 52 is stopped and the measurement of the powdery chemical is started. The solid processing agent used here was one in which two or more components were made into one part by granulation. A running test was carried out in the same manner by attaching this feeder to the automatic developing machine. Although the quantitative accuracy was slightly inferior when compared with the solid processing agents weighed in advance, the component ratio of each part agent was not changed and the photographic performance was stable as compared with the case where the solid processing agents were added for each part.

FIG. 11 is a perspective view of another part-by-part powdery treatment agent supply apparatus showing Comparative Example 1. As shown in FIG. The supply device 60 is divided into a plurality of powdery chemical storage parts 63, and is devised so as to be stored separately for each part as in the conventional concentration kit. Further, there is a dehumidifying device 65 for improving the preservability of the powdery chemical in the storage portion. Rotating body according to the processing information of the photosensitive material
67, the powdery processing agent received on the table 66 is quantitatively transferred to the discharge section 68 for each component and supplied. When a running experiment was carried out using this supply device, the same problem as in Comparative Example 1 was encountered. That is, there is a problem of poor workability due to fine powder when putting the powdery treatment agent into the hopper 64 and a problem of quantitative accuracy. Caking is still there. Further, there is a large problem of stability of the apparatus due to the adhesion of fine powder of the powdery treatment agent to the rotating body, and there is a drawback that the maintainability is extremely poor.

FIG. 12 is a cross-sectional view showing still another supply device of the powdery treatment agent showing an example of the one-part agent of the present invention packaged in a package of two or more components. In the supplying device 70, the powdery processing agent is put into the hopper 71, and the piston 75 moves horizontally (to the right) according to the processing amount of the photosensitive material. It moves to the left), and the quantitative powdery agent is supplied to the constant temperature tank (filter tank) by the discharge part 74. The solid processing agent used here was one in which two or more components were made into one part by granulation. When running experiments using this feeder, the quantitative accuracy is a little inferior when comparing the solid processing agents weighed in advance, but the component ratio of each part agent does not change and the photographic performance is also better than when adding in a batch for each part. It was stable.

FIG. 13 is a cross-sectional view showing still another supply device of the powdery treatment agent showing an example of the one-part agent packaged with two or more components according to the present invention. The supply device 80 has a function of entering the powdery processing agent 88, mounting (loading) the package 81, and automatically opening it by the roller 83, and supplying the powdery chemical by the discharge part 84 by controlling the rotation speed of the screw 82. It is a device that does. Since it has the function of automatically opening the package, fine powder does not fly during opening and mounting, which is good.
Although the quantitative accuracy was slightly inferior when compared with the solid processing agents weighed in advance, the component ratio of each part agent was not changed and the photographic performance was stable as compared with the case where the solid processing agents were added for each part.

FIG. 14 relates to a PTP (Pressure Through Package) packaged solid processing agent charging device according to the pre-divided and weighed solid processing agent of the present invention. (A) is a sectional view of the processing agent supply device, (B) Is a perspective view of the packaging breaking means, (C) is a perspective view of the packaging breaking means, and (D) is a cross-sectional view showing a loading state of the solid processing agent packaged in PTP. PTP for the processing agent storage container
The packaged solid processing agent is stored and may be stored individually in a storage container, or may be a cartridge type in which the solid processing agent is stored in advance. Known materials can be used for PTP packaging, and the solid processing agent is preferably packaged in the form of tablets.The PTP-packaged solid processing agent is supplied from below the storage container, and the photosensitive material is processed in a certain amount. Then, the information of the processing amount detection means is sent to the processing agent supply control means, and the solid processing agent packed in PTP by the motor is pushed out to the wedge-shaped fixing plate and crushed to crush the PTP.
The lower part of the package (mainly using aluminum) is peeled off, and the solid processing agent is put into the processing tank through the input port. Empty PT after throwing in
The P package is further pushed out and discarded from the waste port. As a crushing means, there is a means using a roller other than using a wedge, and can be arbitrarily selected.

FIG. 15 shows an example of a packaged tablet (preliminarily divided and weighed) parts feeder system supply device according to the present invention. The packaging material A or B of the tablet chemical packaged in a package was opened and put in the hopper 101. At that time, fine powder was not generated, and there was no caking, and the handling was good. The stirrer 106 is rotated by the signal of the remaining amount detecting means 109,
The tablets 105 are aligned in the tablet alignment unit 110. The processing agent supply control means 103 operates according to the processing amount of the photosensitive material, and the rotary table 107 conveys the tablets and supplies them from the discharging section 108 to the input section.
The rotary table 107 makes one rotation, the rotary table 107 makes one rotation, and stops at the instruction of the rotary table control means (the tablet can be supplied several times by one instruction). Pills turntable 107
Enter the hole. The packaging material cost is low and the handling is good,
There is an advantage that it can be charged with high accuracy, and in particular, the tablet aligning unit 110 does not cause empty supply by the rotary table and is very efficient. Environmentally friendly due to the reduction of plastic containers. In addition, since there is no fine powder, the inside of the feeder is not contaminated and maintenance-free.

FIG. 16 shows an example of a packaged tablet (preliminarily divided and weighed) parts feeder system supply device 120 according to the present invention. The packaged tablet chemical packaging material (A) or (B) was opened and put in the hopper 133. At that time, fine powder was not generated, and there was no caking, and the handling was good. The movable member 124 is rotated by the signal of the remaining amount detecting means 125, and the tablet chemical is aligned with the tablet aligning unit 129. The movable member 124 stops after a certain amount of alignment. At this time, the sweeper 123 is very effective for the tablets to enter the pocket 122 of the movable part 124 and be aligned with the alignment part 125. The processing agent supply means 126 operates according to the processing amount of the photosensitive material, the first shutter 131 rotates, and the tablet chemical drops downward. Next, the first shutter 131 is rotated in the reverse direction, and one tablet is shuttered 1
Clamp between 31 and 132. The shutter 132 rotates, and the tablet chemical passes through the discharge unit 128 and is supplied to the input unit. Next, the shutter 132 reversely rotates and the shutter 131 closes. The packaging material is inexpensive, easy to handle, and can be put into the container with high precision. Environmentally friendly due to the reduction of plastic containers. In addition, since there is no fine powder, the inside of the feeder is free from contamination and maintenance-free.

FIG. 17 shows a solid processing agent supply device 140 according to the present invention.
FIG. 3 is a perspective view showing an example of the above, in which the solid processing agent is put into the processing tank by peeling off the package of the solid processing agent contained in the package. The front end of the packaging material in which the solid processing agent is wrapped in a four-sided seal is set on the winding shaft 142 which is the fixing means via the roller 141, and when the photosensitive material is processed, it is detected by the processing amount information detecting means. When a certain amount is reached, a signal is sent by the processing agent supply control means and the motor of the winding shaft 142, which is also the processing agent supply means, is moved to move the package containing the solid processing agent by a certain length. , Add the required number of solid processing agents. The means for moving the package may be any means such as detecting a notch previously provided in the package, detecting a print pattern, or detecting a treatment agent for the package, but the point is to accurately detect the required number of solid treatment agents. ,
It is moved by the roller 141 and the winding shaft 142. The roller 141 is installed for the purpose of fixing and positioning the package, and is separated by the two winding shafts and the solid processing agent is put therein. In the case of such a system, the solid processing agent may be granules, pills, tablets, or powders, but tablets are advantageous in that they do not adhere to the seal so much that they can be dispensed with high precision and that stains are unlikely to occur. After the winding is completed, it may be taken directly from the winding shaft, or may be rewound and the package may be discarded together with the cartridge.

FIG. 18 shows an example of a supply device according to a preferred embodiment of the present invention. (A) is a plan view, (B) is a perspective view,
(C) is a top view of various packages. Figures 19 and 20 are
It is a figure which shows the solid processing agent example which was previously divided and weighed and which is used for 18 supply devices. The treating agent 151 is a four-sided sealed package body 152.
It is packaged in the form shown in Fig. 18 (C). The packaging form shown in FIG. 18C is an example of the present invention. The material used for the packaging is a commonly used polymeric resin packaging, aluminum,
Alternatively, a composite material may be used, but the point is that the material has good moisture resistance and low oxygen permeability. The processing agent 151 sealed on all sides is peeled off via the tube 153, and the processing agent 151 is inserted into the charging port 154.
It is thrown into the throwing unit 155 via. Here, the cylinder 153 and the winding shaft 156 act as a treatment agent supply means. Package 1
52 has a structure in which it is wound by a winding shaft 156,
The control of the winding is controlled by the processing agent supplying means which receives a signal from the photosensitive material processing amount detecting means.
When winding, the knob is opened, the tip of the package 151 is set on the winding shaft 156, which is a means for fixing the processing agent storage packaging material, through the tube, and the clamp 157 is twisted.
It is fixed by 158 and wound up. Figure 21 shows solid treatment agent 1
It shows an example of the supply device 160 when 61 is stick-wrapped, (A) is a side sectional view, (B) is a front sectional view. The stick-packed solid processing agent 161 is put into a container 162 which is a container. The stick packaging solid processing agent 161 in the container 162 is turreted by the bridge prevention roller 163 and a roller that also serves as a supply to the turret.
Sent to 164. The stick packaging solid processing agent 161 sent to the turret 164 has both ends fixed by a clamper 165,
After that, it is sent to the cutter part by a rotary motion, the center part of the stick wrap is cut (or cut) by the cutter 166, and further sent to the double-folded plate 167 by rotation.
The stick packaging solid processing agent 161 is bent, and the solid processing agent 161 filled in the stick packaging is put into the chute 168 from the cut portion by the rotary cutter 166. After loading, the scrap is further rotated to reach the scrap drop bar 169, and the clamp opening / closing cam 170 releases the clamper 165. The scrap 171 in the scrap packaging is discarded in the collection chute 172.

FIG. 22 is a sectional view showing one embodiment of the present invention. Processing unit 181 and constant temperature tank 182 forming part of the processing tank
The charging part 185 inside is in communication with each other, and the liquid is forcibly circulated from the lower part of the processing tank by the circulation pump 183, is discharged to the filter part 182, and enters the processing part 181 through the tablet charging part 185. . Processing amount detection means when the photosensitive material is processed
The processing amount is detected by 192, and when a certain processing amount is reached, the motor M2 is driven through the processing amount supply control to supply the tablets weighed in advance to the charging unit 185 in the constant temperature bath 182. There is. The tablets are directly loaded into the storage container 187, and after the loading, the alignment means 188 is driven by the motor M1 in response to a signal from the alignment amount control means 186, the tablets are aligned, and the tablets are supplied to the alignment section 189. The tablets supplied to the arranging unit 189 receive a signal from the processing amount supply control unit 190, and when the motor M2 is driven, the tablets are carried to the upper part of the loading unit by the rotational movement of the supplying unit and are loaded into the loading unit 185. At that time, it is a preferred embodiment that the treatment agent supply means 191 is substantially cut off from the constant temperature bath 182 from the viewpoint of moisture resistance of the tablet. Further, when the tablets are put into the storage container 187, the tablets contained in the containers as shown in FIGS. The container shown in FIGS. 22 (A) and (B) can be made of known materials such as paper and high molecular weight resin aluminum, but it is preferable to use a material having good moisture resistance and low oxygen permeability. .

FIG. 23 is a sectional view showing an example of a solid processing agent supply device 200 individually packaged in a blister. The individual package 202 containing the solid processing agent is loaded into the storage section 203. The disk 201 rotates 180 ° according to the processing amount of the photosensitive material, and then the needle 205
Passes through the individual wrapping 202, passes through the discharge section 204 in the individual wrapping 202, and is supplied to the input section. The empty individual package 202 is discarded through the disposal port. The solid processing agent may be powder or granules, but granules are preferred because the powder adheres to the container. It is easy to handle, and the feeder 200 is free from fine powder stains and maintenance-free.

FIG. 24 is a sectional view showing an example of the present invention. Tablet chemical storage unit 211 according to the processing amount of photosensitive material
It is directly supplied to the charging unit 215 inside the processing tank. The charging section 215 has a solid processing agent filter 216 so that the undissolved processing agent does not directly adhere to the photosensitive material. This filter 2
The material of 16 is not particularly limited. The mesh is not particularly limited either, but it is 10 to 100 depending on the flow of the liquid and the filter effect.
μm is preferred. The effect is almost the same as when the solid processing agent is supplied to the constant temperature bath 212 forming a part of the processing bath. However, the compactness is inferior because there is a separate input part 215 in the processing tank.

Next, FIGS. 25 and 26 show specific examples of packaging of four-sided seals and three-sided seals. However, the present invention is not limited to these. In the sealed packaging shown in FIG. 25 (A), several types of tablets are contained in one packaging unit. In FIG. 25 (B), tablets of different kinds and sizes are individually packaged. Figure 25
(C) is a package of granules or powder. Figure 25
(D) contains one of the same size. Figure
In 25 (E), a plurality of the same chemicals of the same size are contained as small tablets. Figure 25 (F), (G) and figure
26 (H) to (O) are obtained by sealing tablets to form a continuous unit. 26 (P) to (X) show tablets divided into units. 27 (A), (B), and (C) are plan views showing an example of a four-way seal. FIG. 27 (D) shows an example of a three-way seal. Figures 28 (A) and (B) show specific examples of stick packaging, but are not limited to these.

FIG. 29 is a cross-sectional view showing a state in which tablets, granules or powders are sealed and heat-sealed, and then folded into a zigzag and housed in a container.

FIG. 30 shows a specific example of PTP packaging. However, it is not limited to these. FIG. 30 (A) shows a PTP-packed solid treatment agent in the form of a pill, and FIG. 30 (B) shows a state in which a plurality of tablets of the treatment agent are packaged.
FIG. 30 (C) shows a state in which tablets, granules, or powders are placed in tandem. FIG. 30 (D) shows these packages connected in a row. Alternatively, it may be a blister-like one shown in FIG.

FIG. 31 shows a specific example of collective packaging. However, it is not limited to these. FIG. 31 (A) shows the solid processing agent housed in a cylindrical container, and FIG. 31 (B) shows the solid processing agent housed in a flexible two-sided or three-way sealed bag.
FIG. 31 (C) shows a bag containing the solid processing agent, which is sealed on the other hand.

32 and 33 are perspective views showing a specific example of the cartridge. These cartridges can be mounted in the feeder of the automatic developing machine of the present invention without changing the packaging material containing the solid processing agent. As the material, any of the compounds described above can be used. When the amount of the solid processing agent decreases, it is preferable that it does not collapse so as not to hinder the supply. FIG. 32 (A) shows a tablet containing a tablet in a cylindrical cartridge, and FIG. 32 (B) shows a tablet containing granules or powder. 32 (C), (D)
FIG. 2A is a perspective view and a sectional view showing a mode in which a solid processing agent is contained in a box-shaped cartridge having an opening / closing lid.

In FIG. 33, tablets, granules or powders are stored in a rotatable container having a partition wall and further stored in an outer cylinder (main body), and a predetermined amount is dropped from the opening. FIG. 33 (A) shows a type in which the rotating shaft is supported horizontally,
FIG. 33 (B) shows a type in which the rotary shaft is vertically supported.
The present invention is not limited to these specific examples.

Further, FIGS. 34 (a) and (b) and FIGS. 35 (a) and 35 (b)
Another embodiment of FIGS. 36, 37 and 38 will be described.
34 (a) and 34 (b) show a "U-shaped" half punching method. When the photosensitive material is processed, it is detected by the processing amount information detecting means, and when a certain amount is reached, a signal is sent by the processing agent supply control means and the conveying roller 100 is rotated, so that the solid processing agent 10 is contained. The package 801 shown in FIG. 35 (a) is shown in FIG.
Move to the position shown in (a) and stop. The means for moving the packaging body 801 is a means for detecting a notch previously provided in the packaging body 801, a detection of a printed pattern or an eye mark, and a packaging body 80.
Any means such as detection of the processing agent 10 of 1 may be used, but the point is to detect the required number of solid processing agents 10 with high accuracy. Next in Figure 34.
As shown in (b), the punch male die 300 moves downward to cut the package 801 and the solid processing agent 10 is loaded into the processing tank of the automatic processor through the loading port 901 in FIG. 35 (a). The cut end cut by the punch male die 300 is a punch shape 601 as shown in FIG. 35 (b).
It becomes a U-shaped like. In the case of such a method, solid treatment agent
10 may be powders, granules, or tablets, but preferably punch male type, and tablets to which chemicals are hard to attach are preferable. Further, the tablets 10 do not adhere much to the package, and therefore stains do not easily occur, and are safe for the user to handle. The used packages 801 can be put together in the waste box 102 and discarded. As the waste box 102, it is preferable to reuse the used package storage box 701.

36 and 37 show the cut-off means of the package 11. When the photosensitive material is processed, it is detected by the processing amount information detecting means, and when a certain amount is reached, a signal is sent by the processing agent supply control means and the conveying roller 201 is rotated, and the package containing the solid processing agent 10 is supplied. The solid processing agent 10 moves the body 11 to a position above the processing tank filter section 702 and stops. At this time, the tip of the package 11 has entered the ironing roller 401. The means for moving the packaging body may be any means such as a means for detecting a notch previously provided in the packaging body 11, a printed pattern detection, a packaging body processing detection, etc.
Should be detected accurately. Next is a ceramic cutter
201 cuts the package 11. When the cutting is completed, the squeezing roller 401 and the conveying roller 501 rotate, and the solid processing agent 10 is squeezed by the squeezing roller 401, passes through the discharge port, and is put into the processing tank filter section 702 of the automatic processor. The cut waste package 802 is discharged from the transport roller 501 and is discarded in the waste box 602.
to go into. The waste box 602 is preferably a reused box for a used package. In the case of such a system, the solid processing agent 10 may be a powder, granules, or tablets, but it is preferable to use tablets in which a chemical is not attached to the ceramic cutter 201. Further, the tablets have an advantage that they do not adhere to the package 11 so much that stains are less likely to occur. Used packaging 11 is a waste box
It can enter in 602 and can be discarded together.

FIGS. 38 (a) and 38 (b) show a two-division cutting method for the continuous package 603. When the photosensitive material is processed, it is detected by the processing amount information detecting means, and when a certain amount is reached, a signal is sent by the processing agent supplying means and the conveying roller 502.
At the same time as the rotation, the circular blade 301 made of ceramic or stainless steel rotates, and the lower part of the continuous package 603 is cut in two, and the solid processing agent 10 is charged. This repackaging body 603 to divide into two
Is spread on both sides by suction on the suction guide 202, and the solid processing agent 10 inside is easily dropped. The empty package 603 without the solid processing 10 is moved by the transport roller 401 at the time of the next introduction of the solid processing agent 10 and is discarded in the package storage box 101. In addition to the above-mentioned means, this two-division may be made by attaching a notch or the like to the continuous package, and tearing while winding with a roller. In the case of such a system, the solid processing agent 10 may be any of powder, granules, and tablets, but it is preferable to use tablets in which the chemical is not attached to the punch male mold. Further, the tablet does not adhere to the seal of the package so much that the stain is less likely to occur. The used packages 603 can be put together in the package storage box 101 and discarded.

[0177]

As described above, the automatic developing machine for silver halide photographic light-sensitive materials of the present invention is deficient in photographic materials because the solid processing agent which has been previously divided and weighed is directly added to the processing tank and dissolved. The photographic performance can be made uniform by eluting or supplementing the components, and by supplementing the required amount of supplementary water separately as needed. It is no longer necessary for the user to create a replenisher solution for a certain period of time, and the performance of the processing solution can be improved by automatically adding the solid processing agent in advance according to the processing amount of the photographic material. Maintained constant.

The replenishment tank volume is 4 to 4 for color negative.
Since 5 kinds of liquids are required, 40 to 50 liters are not required, and it can be made compact. In the past, the replenisher in the replenisher tank was floated, and the storage stability was not guaranteed for about 2 weeks, but in the age of low replenishment, 10 liters of replenisher was used for more than 1 month, and its storability was improved. What was a low and serious problem would be solved all at once.

In addition, the replenishers in the low replenishment era were all made thicker by using the performance up to the solubility limit of the chemicals, and each of the replenishers had a concentration of 1.4 to 2 times that of the solution used. However, it was in a supersaturated state. Therefore, during storage in winter, there were problems such as precipitation of crystals and generation of tar and damage to photographic materials to be processed. It will be understood that the present invention solves all such problems. That is, in the present invention, only a liquid having a low concentration such as the processing liquid used is present. This is because the solid processing agent is used to make up for the shortage, and therefore, it is basically impossible for the solid processing agent to reach a high concentration beyond the processing solution used.

For the above reasons, the conventional replenishing means could not reduce the replenishing rate because the replenishing solution could not be further concentrated due to its solubility limit. In particular, the color developing replenisher for color paper and the stability of the bleach-fixing solution could not be reduced because the stability was too low.The low replenishment of the bleach-fixing solution can be promoted by the solid processing agent replenishing means of the present invention. Become. Furthermore,
All of these are achieved and realized by the replenishing means of the present invention in which there is no replenisher. Solid processing agents are less dangerous to transport and do not require robust containers. There are no transportation safety regulations such as liquid dangerous goods, and packaging can be simplified. It has the advantages of high safety in transportation and handling in shops and without damaging or soiling human body or clothes.

However, solid type kits were once popular because of the drawback that solid processing agents are difficult to dissolve, but recently, most of them are liquid type and supplied as liquids because the dissolution work takes time. It was. As a result of diligent research on this point, the present inventors put a solid processing agent, which was divided and weighed in a small amount, directly into a processing solution tank whose temperature was controlled to a constant temperature, so that it was stable without any problem even if dissolved over time. It has been discovered that replenishment work for maintaining the photographic performance can be performed, that is, conventionally, it is common sense that the replenisher solution once completely dissolved must be stored in the replenisher tank and injected into the processing tank as necessary to maintain the components. The replenishing solution kit which has been considered to be impossible is a solid processing agent which is divided and weighed in advance in accordance with the processing amount information of the silver halide photographic light-sensitive material according to the present invention. , And by supplying fixed amount of replenishing water to a part of the same processing tank periodically as needed, complicated chemical solution work of user by chemical replenisher is eliminated and automatic developer replenishment is done. It has been achieved to eliminate the dangerous liquid chemical kits and the conventional chemical bottles containing them, and since there is no replenishment tank, the replenisher does not exist and the life time of the liquid is significantly improved. It is possible to dramatically improve the processing stability.

A method of replenishing ABC3 package of a concentrated liquid kit called AR replenishment and replenishment water directly by a bellows metering pump while replenishing the replenisher solution in advance has been adopted. Although it has been implemented, consideration has been given to adding 4 components while mixing them in advance instead of directly adding them to the treatment tank, and this has not been done with a solid processing agent. .

[Brief description of drawings]

FIG. 1 is a schematic configuration diagram of a printer processor in which an automatic developing machine and a photo printing machine are integrally configured.

FIG. 2 is a cross-sectional view of a processing agent input unit and a processing agent supply unit of an automatic processor.

FIG. 3 is a cross-sectional view of a processing agent input unit and a processing agent supply unit to which a replenishment water supply unit of the automatic processor is added.

FIG. 4 is a plan view of the automatic processor.

FIG. 5 is a block diagram including a control unit of the automatic processor.

FIG. 6 is a block diagram in which a melting table of control means is added.

FIG. 7 is a configuration diagram of a dissolution test unit.

FIG. 8 is a configuration diagram of a dissolution test unit.

FIG. 9 is a characteristic diagram of replenishment amount and concentration rate.

FIG. 10 is a cross-sectional view of a powdery processing agent supply device of a comparative example and a perspective view of a package.

FIG. 11 is a perspective view of a powdery processing agent supply device.

FIG. 12 is a cross-sectional view of another powdery treatment agent supply device.

FIG. 13 is a cross-sectional view showing another embodiment of the powdery treatment agent supply device.

FIG. 14 is a sectional view and a perspective view of a PTP packaging treatment agent supply device according to the present invention.

FIG. 15 is a cross-sectional view showing another embodiment of the supply device.

FIG. 16 is a sectional view showing still another embodiment of the supply device.

FIG. 17 is a perspective view showing still another embodiment of the supply device.

FIG. 18 is a plan view and a perspective view of a supply device and a plan view of a package.

FIG. 19 is a diagram showing an example of a solid processing agent used in the supply device of FIG.

20 is a diagram showing an example of a solid processing agent used in the supply device of FIG. 18 and divided and weighed in advance.

FIG. 21 is a side sectional view and a front sectional view of the supply device.

FIG. 22 is a cross-sectional view of a supply device and a perspective view of a package.

FIG. 23 is a cross-sectional view of a solid processing agent supply device individually packaged in a blister.

FIG. 24 is a cross-sectional view showing an example of adding a solid processing agent directly to a processing tank.

FIG. 25 is a plan view of the seal packaging.

FIG. 26 is a plan view of the seal packaging.

FIG. 27 is a plan view showing a specific example of a three-side seal and four-side seal seal packaging.

FIG. 28 is a plan view showing a specific example of stick packaging.

FIG. 29 is a cross-sectional view showing another specific example of stick packaging.

FIG. 30 is a diagram showing a specific example of PTP packaging.

FIG. 31 is a diagram showing a specific example of collective packaging.

FIG. 32 is a diagram showing a specific example of a cartridge.

FIG. 33 is a perspective view showing another specific example of the cartridge.

FIG. 34 is a device for cutting the packaging body by cutting it into a U-shape.

35 is a perspective view of a device for half-drawing the package of FIG. 34 into a U-shape.

FIG. 36 is an apparatus showing a method of cutting off a package.

FIG. 37 is a perspective view of the device showing the trimming method of FIG. 35.

FIG. 38 is an apparatus showing a two-division cutting method for a continuous package.

[Explanation of symbols]

 1 Treatment Tank 1A to 1E Treatment Tank 1R Rack 2 Treatment Section 3 Filter 4 Circulation Pipe 5 Circulation Pump 6 Drainage Pipe 7 Heater 8 Treatment Quantity Information Detecting Means 9 Treatment Agent Supply Control Means 10 Extrusion Member 11 Solid Treatment Agent Injecting Section 12 Partition Wall 13 Tablet 13 'Solid photographic processing agent 14 Filtration part (division) 14A Stirring blade 14B Stirring blade 14C Shearing gear 14D Vibrator 14E Magnetic rotary blade 14F Rotating magnet body 14L Transmission mechanism 14M Motor 14N Partition member 14P Injection pump 15 Cartridge 16 Lead Line 17 Treatment agent supply means 17 'Treatment agent supply part 18 Push claw 19 Cam 19' Pinion gear 21 Tablet pressing spring 23 Preprogrammed evaporative rehydration setting means 24 Tablet stopper 25 Screw 27 Screw 28 Container 29 Treatment agent guide part 32 Hot water replenishing device 33 Solenoid valve 35 Drying section 36 Replenishment pipe 41 Pipe (for replenishment water) 42 Replenishment water supply means 43 Replenishment tank

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[Procedure amendment]

[Submission date] January 12, 1993

[Procedure Amendment 1]

[Document name to be corrected] Drawing

[Name of item to be corrected] Fig. 4

[Correction method] Change

[Correction content]

[Figure 4]

Claims (7)

[Claims] 1. A solid processing agent containing a plurality of components is a solid processing agent divided and weighed in advance in a replenishment unit, or a batch solid processing agent in which all components are uniform, and the solid processing agent is a solid processing agent. In the automatic processor for silver halide photographic light-sensitive material, which is stored in a processing tank and uses gravity to drop into the processing tank from below, and replenishing water supplying means for supplying water to the processing tank, the solid processing The replenishment is controlled so that the amount of the replenishing agent supplied at one time is in the range of 0.5 to 30 g, and the replenishing water supply of the replenishing water supply means is averaged in accordance with the processing amount of the silver halide photographic light-sensitive material. An automatic developing machine for a silver halide photographic light-sensitive material, comprising a water supply control means. 2. The method according to claim 1, further comprising: a unit for detecting and integrating a processing amount of the silver halide photographic light-sensitive material, and a storage unit for storing the integrated amount information. Automatic processor for silver halide photographic light-sensitive materials. 3. The automatic developing machine for silver halide photographic light-sensitive materials according to claim 1, wherein the unit of supply of the replenishing water supplied by averaging is 2 ml to 100 ml. . 4. The automatic developing machine for silver halide photographic light-sensitive materials according to claim 1, wherein the solid processing agent is a processing agent which is divided and weighed in advance by a moisture-proof material. 5. The halogen according to any one of claims 1 to 4, wherein the solid processing agent is a granular or tablet-formed tablet formed by a granulation step and comprises a uniform component. Automatic processor for silver halide photographic materials. 6. The automatic developing machine for silver halide photographic light-sensitive materials according to claim 1, wherein the replenishing water is provided with antifungal means selected from the following group. . (Group) Chelating agent addition means Antifungal agent addition means Deionization treatment means Ultraviolet irradiation means Magnetic treatment means Ultrasonic treatment means Electrolytic sterilization means Silver ion release means Air foaming means 7. The halogenated product according to any one of claims 1 to 6, wherein the pre-divided and weighed solid processing agent contains all necessary components in a unit composed of a plurality of uniform tablets. Automatic developing machine for silver photographic light-sensitive materials.