JPH06161076A - 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 and more specifically the automatic developing machine with which the machine is made compact, its workability is improved, the lower replenishing is facilitated and the stable photographic performance is obtd. CONSTITUTION:This automatic developing machine has at least one processing tanks 1 which house exposed silver halide photographic sensitive materials, a processing agent charging section in which these processing tanks 1 and processing liquid pass, a housing means 15 for housing solid processing agents 13 which are previously divided and weighed to a specified weight and are seal packaged at >=3 sides, a supplying means 17 which charges the solid processing agents 13, a processing quantity detecting means 8 which detects the processing information of the silver halide photographic sensitive materials and a control means which charges the solid processing agents 13 by controlling and operating the supplying means 17 according to the information on the processing quantity detected by the detecting means 8. The solid processing agent supplying means 17 charges the solid processing agents after unsealing the seal packaged materials.

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 sometimes referred to simply as "developing machine"). The present invention relates to an automatic developing machine which has a significantly improved workability and which dramatically improves chemical stability.

[0002]

2. Description of the Related Art Silver halide color photographic light-sensitive materials (hereinafter sometimes referred to as light-sensitive materials or photographic materials) are
After the exposure, it is processed by steps such as development, desilvering, washing and stabilization. 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. Each treatment liquid is usually 30 ~
The temperature is adjusted to 40 ° C., and the light-sensitive material is dipped in these processing solutions and processed.

Such processing is usually carried out by sequentially conveying the inside of a processing tank containing the above processing liquid by an automatic developing machine (hereinafter referred to as an automatic processor) or the like.

When referred to as an automatic developing machine, it has a developing section, a fixing section, a desilvering section, a washing or stabilizing section, and a drying section, and each processing tank section automatically conveys the photographic light-sensitive material. It generally refers to a developing machine having means.

In the case of processing with such an automatic developing machine, a method of replenishing the processing agent is generally widely used in order to keep the activity of the processing solution in the processing tank constant.

As a method for replenishing the treating agent, a method of preparing a replenishing solution in which the treating agent is dissolved is widely used.

[0008] Specifically, the replenishing solution prepared in advance is supplied from the replenishing tank to the processing tank at appropriate time to perform the processing operation.

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, the replenishing tank is installed in a constant amount in a 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, a processing agent for silver halide photographic light-sensitive materials (hereinafter sometimes referred to as a photographic processing agent) is commercially available in the form of powder or liquid.
In the case of a powder, it is prepared by manually dissolving it in a fixed amount of water, and in the case of a liquid, it is concentrated so that a fixed amount of water is added and the mixture is simply stirred and diluted before use.

The replenishment tank may be installed next to the automatic machine, and it is necessary to secure a considerable space. In addition, even in the minilab, which has been increasing rapidly in recent years, a replenishment tank is built into the machine itself, but at least 5L-10
It is necessary for each of the L liquids, and it is necessary to secure such a space for the replenishment tank.

Replenishing processing agents are divided into several parts in order 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 for improving workability, and most of them are extremely dangerous aqueous solutions with a pH of 2.0 or less or 12.0 or more. Many of them are very dangerous and are often strong oxidizers or reducing agents, and they have extremely dangerous corrosiveness when transported by ship or aircraft. 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. However, recently, the replenishment amount of each processing solution has been lowered, and 10 L 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 replenishing solution in the replenishing tank is much more exposed to air than the treating solution in the processing tank and is deteriorated. is happening. Therefore, 5L refill tank
The device is designed to be small and the storage unit of the replenishment kit is set to 5 L. In this case, there is a drawback that a packaging material is further required.

In addition, taking the color developing replenisher for color paper as an example, when a color developing replenisher for color paper is prepared, a certain amount of water is put into a replenishing tank, and then a preservative-containing concentration 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 the color developing replenisher prepared from the concentration kit or the powder also has some problems in the replenishing tank. 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 method for preparing a replenishing solution using a commonly used concentration kit or the method for preparing a replenishing solution using a dusting agent is exemplified by a color developing solution for color paper. There are the above-mentioned problems, and there are similar problems 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 thickened while the replenisher is being made lower and faster, and the recent replenisher is usually concentrated to the solubility limit. This means that the storability of the replenisher only deteriorates, and there are many practical problems such as crystal precipitation.

On the other hand, in addition to the method of preparing a replenisher using the concentration kit or powder as described above, a method of directly replenishing the concentration kit is known.

In this method, in order to improve the inefficiency of the dissolving 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. is there. Certainly, this method does not require a liquid preparation operation as compared with the method of adjusting the replenisher solution from the above-mentioned concentration kit or powder. Alternatively, since a replenisher is not prepared, the problem of storability is eliminated.

However, the above method also has 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 method,
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 the waste poly container do not change even if the waste poly container is provided with the concentration kit.

There are some proposals for eliminating the plastic container and improving the chemical stability of the replenisher by methods other than the above.

For example, Japanese Patent Application Laid-Open No. 58-11032 discloses a technique of encapsulating a developing component in microcapsules, and Japanese Patent Application Laid-Open No.
-61837 discloses a photographic tablet containing a disintegrant. Furthermore, JP-A Nos. 2-109042 and 2-109043,
3-39735 and 3-39739 disclose a method of using a granulated photographic processing agent having a certain average particle diameter.

The photographic tablet containing the disintegrant described in JP-A-51-61837 is merely a tablet that can be easily dissolved in water, and the solid processing agent is directly added to the processing tank of the present invention. The idea of dissolution cannot be recalled at all.

Further, Japanese Patent Laid-Open No. 2-09042 describes a granulated photographic processing agent having a certain average particle size.

However, the above-mentioned publication proposes a compact automatic developing machine which eliminates the work of dissolving the replenisher to sufficiently simplify the workability and obtain stable photographic performance in the automatic processor and eliminates the replenishing tank. is not.

On the other hand, as a method of eliminating the need for a prior melting operation, Japanese Patent Laid-Open No. 3-11344 discloses extruding a paste-like part agent from each unit container in an amount corresponding to the mixing ratio of the part agent. Although a technology for accurately adjusting and supplying the part agent by diluting it to a predetermined concentration is disclosed, this method surely reduces the dissolution work or almost eliminates the dissolution work, but it is a paste form. Since the part agent contains a solvent, it lacks stability, and it is difficult to extrude a certain amount for a long period of time. If the part agent is not used frequently, the nozzle is likely to be clogged, and 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.

[0035] Further, Japanese Utility Model Laid-Open No. 1-85732 discloses an automatic developing machine having means for adding a tablet type antibacterial agent to a stabilizing solution. Since there is no particular problem, it is not necessary to control the feeding, and this does not remind the treating agent replenishment control means.
This is not mandatory because the purpose is to preserve the liquid itself.

WO 91-07698 and WO 91-07699 disclose a method in which CD-3 or CD-4 is added as a solid and the other components are added 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 the developing solution by an ion exchange resin, an alkaline agent activator or solid or small amount which is a deficient component. It is a method for adding a concentrated color developing agent and adding components without increasing the volume.

Further, in Japanese Patent Laid-Open No. 4-237045, a powdery treating agent is set on an automatic developing machine for each part, and while being weighed in necessary amounts, each is directly charged into a treatment tank, and water is added as dissolved water at the time of charging. A technique that may be added is disclosed.

Certainly, with this technique, the conventional work of dissolving the replenisher is eliminated and the replenishment tank is eliminated, so that the automatic developing machine can be made compact.

However, this method is a system in which the powdery processing agent is weighed and charged into the processing tank, and the accuracy of the weighing tends to vary. Further, the position where the powdery treatment agent is set is the upper portion of the treatment tank, and the high humidity environment is large. Therefore, in this method, it is difficult to completely prevent the set granular treatment agent from moisture, and the moisture absorption of the powdery treatment agent causes
It is not perfect because it causes deterioration of weighing accuracy and storage stability of the treatment agent.

Therefore, in WO-91-07332, the solid processing agent is defined as PTP.
(Pressver Through Package) A technique is disclosed in which the solid processing agent is packaged, extruded from a PTP package, and supplied to a processing tank.

Although this method surely improves the moisture resistance of the solid processing agent and eliminates the work of dissolving the replenisher,
Due to the nature of the method, the packaging material requires an aluminum sealant, which not only increases costs, but also requires too much space to stack in series and requires space, which easily causes malfunctions during punching. Since maintenance is difficult, it is completely different from the maintenance-free object of the present invention.

In the present invention, the replenishment of the treating agent is carried out only by the operation of introducing the preliminarily divided and weighed solid treating agent into the treating tank, and by dissolving in the treating tank, the operation of preliminarily dissolving the replenishing solution is eliminated and maintenance-free. The purpose of the present invention is to achieve a replenishing system at low cost, and the purpose is completely different from the above invention, and the present invention cannot be inferred.

[0043]

SUMMARY OF THE INVENTION The first object of the present invention is to:
In addition, it is to achieve the practical application of an automatic developing machine that eliminates liquid chemicals that pose transport and handling hazards and enables solid chemicals to be used without complicated operations for users.

Secondly, the purpose is to achieve an automatic processor in which a fully automatic replenishment system is completed at a low cost by eliminating the user's own work of dissolving the concentration kit.

Thirdly, there is the achievement of an automatic developing machine which is compact in size by eliminating 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.

The sixth object is to achieve moisture proofing of the processing agent to be replenished at a low cost, and to achieve an automatic developing system with greatly improved processing stability.

[0049]

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.

(1) At least one processing bath containing a processing liquid for processing the exposed silver halide light-sensitive material,
This treatment tank and a treatment agent feeding part through which the treatment liquid flows, a storage means for storing a solid treatment agent, which has been divided and weighed in advance into a fixed amount and sealed and packaged on three or more sides, and a supply means for feeding the solid treatment agent. A processing amount detection means for detecting processing information of the silver halide photographic light-sensitive material, and a solid processing agent for controlling the supply means in accordance with the processing amount information of the silver halide photographic light-sensitive material detected by the detection means. An automatic developing machine for a silver halide photographic light-sensitive material, characterized in that the solid processing agent supply means inputs the solid processing agent after opening the seal packaging material.

(2) The automatic developing machine for silver halide photographic light-sensitive material as described in (1), wherein the processing agent supply means charges the solid processing agent by gravity after opening the seal packaging material.

(3) The processing agent supply means inputs the solid processing agent by cutting or cutting a part of the seal packaging material (1).
~ An automatic developing machine for silver halide photographic light-sensitive materials as described in (2).

(4) The amount of solid processing agent added at one time is
The automatic developing machine for silver halide photographic light-sensitive materials as described in (1), which is 0.1 g to 50 g.

(5) The automatic processor for silver halide photographic light-sensitive material as described in (2), wherein the solid processing agent is a granular or tablet-formed tablet formed by a granulating step.

(6) A processing tank to which the solid processing agent is supplied is connected to a processing section for processing the silver halide light-sensitive material and the processing section, and a processing agent charging section for charging and dissolving the solid processing agent is provided. The automatic developing machine for silver halide photographic light-sensitive materials according to (1), which further comprises a circulating means for circulating a processing liquid between the processing section and the processing agent feeding section.

(7) Halogen according to any one of (1) to (6), characterized in that it comprises a replenishing water supply means for replenishing replenishing water into the processing tank, the operation of which is controlled according to information on the processing amount of the photographic light-sensitive material. Automatic processor for silver halide photographic materials.

[0057]

The present inventors have conducted enormous experiments on the direct addition of the solidifying treatment agent to the tank, and have determined the optimum replenishment amount of the treatment agent to be added at one time so as not to change the photographic performance of each treatment solution. I asked. It was thought that this optimum replenishment amount depended on the size of the processing tank of the automatic processor, that is, the capacity of the processing solution, but by making good use of the characteristic of the solid chemical that is difficult to dissolve, even if added at once, it can be rapidly added. It has been found that the concentration does not increase, and replenishing water can be injected in accordance with the dissolution, 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.

The amount of the processing agent to be added at one time is preferably 0.1 to 50 g, 1 to 20 g for the color developing solution, 5 to 50 g for the fixing solution and the bleach-fixing solution, and 0.1 to 10 g for the stabilizing solution.
However, in the black-and-white developer, 0.5 to 20 g is particularly preferable, and the solid processing agent in this range is directly added to the processing tank of a general small-sized developing machine and does not adversely affect the photographic state even when processed while slowly dissolving. . Because the solid processing agent does not dissolve rapidly as described above, it dissolves slowly, so even if the amount added at one time is large, the composition is balanced with the amount consumed during processing and stable processing performance is achieved. It is because it shows. It has been found that the photographic performance can also be made constant by injecting replenishing water according to the dissolution. This thing is
It was an amazing discovery that no one noticed. Further, in the present invention, the solid processing agent is directly charged into the processing tank, but the processing liquid is always temperature-controlled to the processing temperature and maintained at a substantially constant temperature. That is, since the dissolution speed is almost constant throughout the year, the calculated addition of the solid processing agent and the balance of the components can be achieved. It has been discovered that this has the great advantage that the insolubility phenomenon seen when dissolving in cold water does not appear. The insolubilization phenomenon named by the present inventors is a solidification phenomenon that occurs when the solid processing agent is poured into cold water at once and is slowly or hardly stirred, and refers to a vitrification state at first glance. Then, it was found that even if it was vigorously stirred, it was not dissolved for a long time. On the other hand, in the hot water dissolution at the processing temperature of the automatic processor, a phenomenon was discovered in which the solid processing agents were sequentially dissolved even when they were added, and the present invention was completed.

In the present invention, it is desirable to provide a replenishing water supply means, but it is desirable to similarly control it according to the processing amount detection stage of the photographic light-sensitive material necessary for controlling the input of the solid processing agent. However, it should be emphasized that the makeup water is not water for dissolving the solid processing agent. That is, the solid processing agent is intended to supplement the consumption component that was originally lacking by the treatment, and the replenishing water is intended to dilute the reaction-suppressing component eluted by the treatment so as to keep the photographic performance constant. Is the exact opposite. In the past, water happened to be used to dissolve chemicals, but the original purpose was to supplement the water carried out by the photographic material and the water evaporated from the surface of the tank, as described above, while at the same time storing components that elute by the reaction. It is for thinning. Therefore, although it can be controlled separately from the addition of 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 processing agent is directly charged into the processing tank, the amount of water required for adjusting the replenisher in the related art is unnecessary, and as a result, the overflow is reduced, which has a large side effect. I understood it.
In the past, it was common knowledge that the replenisher had to be adjusted in advance, so the concentration of the replenisher was made as high as possible to compensate the components. Even if it is known that the thicker the concentration, the more the replenishment amount can be reduced, and the overflow waste liquid which is an environmental problem can be reduced, the solubility of the treatment chemicals becomes a large barrier, which cannot be achieved. According to the present invention, the concentration of the chemical is substantially only in the tank liquid, there is no high-concentration state above the tank liquid, and the replenishment is only the necessary treatment chemicals, so it is possible to replenish without any overflow.

However, as described above, it is preferable to use replenishing water in order to reduce the accumulation of the reaction-suppressing component, particularly the concentration of halide ions in the developing solution and the 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 tank surface for the purpose of diluting these reaction inhibiting components, which is the processing stability of the present invention. And contribute significantly.

Therefore, the control information used to supply the replenishing water is the processing amount (for example, 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 this is a term management method. The reason for this is that as the low replenishment rate is advanced, the treatment agent component becomes more concentrated due to the effect of evaporation from each tank, which is a big problem. Generally, in order to correct the evaporation, it is the most preferable method to dilute the replenisher and replenish it in a large amount, but this has a drawback that it causes an increase in overflow waste liquid and is environmentally unfavorable, and therefore low replenishment has been promoted. It was If the replenisher is used for evaporation correction, it is the same as if the replenisher is not processed but the replenisher enters. So the morning liquid level went down,
The method of replenishing water and adjusting the liquid level was common,
This is not to replenish the evaporation with water, but only to add water to the treatment liquid in the tank whose temperature has changed and the volume has been reduced, and no fundamental solution has been reached.

The correct evaporation correction is to ensure that the constituents do not change except by consumption by the photographic material, and the evaporated water produced by the tank liquid temperature and the tank surface vapor pressure is evaporated with or without treatment. It is to supply according to quantity.

That is, in the present invention, the supply of makeup water is performed for the following three purposes. For the purpose of diluting the accumulated harmful inhibitory components that elute due to the reaction when the light-sensitive material is processed, so as to keep the concentration constant, dilute the water taken out by the photographic material processed for 1 or unnecessary chemicals brought in from the previous solution. It is replenished for the purpose of diluting and for replenishing water evaporated from the tank surface, and the information necessary for the above purpose is detected and the water replenishing means preset by this information Controlled and executed. This method is a new method that has never existed in the past and is made possible by the present invention. It has been found that this water replenishing means of the present invention dramatically improves treatment stability. In the present invention, the solid processing agent is divided and weighed in advance into a predetermined amount and a fixed amount. Therefore, the processing in the automatic processor of the present invention has high replenishment accuracy and exhibits extremely stable continuous processing performance. Pre-divided weighing means that the processing agent is already weighed in a predetermined amount before being stored in the automatic developing machine or before the packaging material containing the processing agent is set in the fixing means. For example, it refers to a mode in which tablets or pills having a predetermined size are formed, and a mode in which granules or powders are subdivided into predetermined amounts and packaged. It does not include a mode in which the powder or granules are put in the storage means and the amount of each input is measured at the time of supply. In the conventional replenishment liquid 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, the solid processing agent in the case of the present invention is produced by being weighed and divided into a fixed amount at a processing agent production factory, for example, and the replenishment control is ON / OFF control whether the solid processing agent is fed or not. There is no variation due to. Therefore, the accuracy of supplying the processing agent is remarkably high, and the stable processing performance can be obtained also by this. 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. In addition, the object of the present invention can be achieved even if a safe substance such as water that does not become a dangerous substance is used in combination with a liquid substance.

In the present invention, the solid processing agent is characterized in that it is divided and weighed in advance, and each is packaged in a package that seals on three or more sides. It is possible to prevent moisture absorption, and a stable supply of the solid processing agent can be realized.

The solid processing agent referred to in the present invention includes the powder processing agents as described above and the solid processing agents such as tablets, pills and granules. Pastes and slurries are not included in the solid processing composition of the present invention, except for those which are semi-liquid and have poor storage stability and are subject to regulations that pose a risk of transportation.

The powder in the present invention refers to an aggregate of fine grain crystals. The granules referred to in the present invention are obtained by adding a granulation step to powder, and are granular materials having a particle size of 50 to 5000 μm. The tablet in the present invention refers to a powder or granules compression-molded into a certain shape.

The present invention will be described in more detail below.

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 a water-soluble binder is preliminarily formed on the surface of the photographic processing agent. Any means such as forming a coating layer by spraying can be adopted (Japanese Patent Application No. 2-135887, No. 2-203165,
2-203166, 2-203167, 2-203168, 2-304
See No. 09). A preferable tablet production method is a method in which a powdery solid processing agent is granulated and then a tableting step is performed to form the tablet. 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.

As the granulation method for tablet formation, known methods such as rolling granulation, extrusion granulation, compression granulation, crushing granulation, stirring granulation, fluidized bed granulation and spray drying granulation are used. Can be done.
In order to form tablets, the average particle size of the obtained granules is 100 to 800 μm, because when the granules are mixed and compressed under pressure, non-uniformity of the components, so-called segregation does not easily occur. It is preferable to use one, more preferably 200 to 750 μm
Is. Furthermore, the particle size distribution is ± 10 for 60% or more of the granulated particles.
Those having a deviation of 0 to 150 μm are preferable. 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.

A method for producing a tablet processing agent is described in, for example, JP-A-51
-61837, 54-155038, 52-88025, British Patent 121
It can be produced by a general method described in the specification such as 3808, and the granule treating agent is, for example, JP-A-2-19042,
It can be produced by a general method 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. 729862, and German Patent No. 3738361, and the like.

The bulk densities of the above solid processing agents are tablets in view of their solubility and the effects of the object of the present invention.
In terms of the strength of 1.0g / cm ³ ~2.5g / cm ³ is preferably 1.0 g / cm ³ greater than the resulting solid, from the viewpoint of solubility of the solid product obtained as 2.5 g / cm ³ less than preferable. When the solid processing agent is granules or powder, the bulk density is preferably 0.40 to 0.95 g / cm ³ .

The solid processing agents used in the present invention are used in photographic processing agents such as color developing agents, black-and-white developing agents, bleaching agents, fixing agents, bleach-fixing agents and stabilizers. The color developing agent has a large stabilizing effect.

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 which cause a chemical reaction with each other and also contains a harmful component, the effect of the present invention is most remarkably exhibited. More preferably, in addition to the color developing agent, the bleach-fixing agent, or the bleaching agent and the 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 a part of the components of a 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 the processing agents to be replenished to the respective processing tanks 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 a preferable method 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, all of the alkaline agent, the color developing agent and the reducing agent are converted into solid processing agents, and in the case of tablets, at least 3 agents or less, most preferably 1 agent, is used in the present invention. 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 or granules be packed in the same package.

In the present invention, the solid processing agent is individually packaged in a package characterized by sealing on three sides or more, whereby the moisture resistance of the solid processing agent is achieved. The materials used for this package are shown below.

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 films are usually laminated and adhered to each other, 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-deposited synthetic resin between the above synthetic resin films.

Further, the total oxygen permeability of these laminated films is preferably 50 ml / m ² 24 hr / atm or less (at 20 ° C. and 65% RH), more preferably 30 ml / m ² 24 hr / atm or less.

The total film thickness of these laminated films is 1 to 2000.
μm, more preferably 10 to 1000 μm, and even more preferably
It is preferably 50 to 1000 μm.

The above synthetic resin film may be a single layer (polymer) resin film, or a laminate of two or more (polymer)
It may be a resin film.

Examples of the one-layer polymer resin film suitable for 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.
It can be preferably used in the present invention. Next, as a laminated polymer resin film that meets the conditions of the present invention, for example, (4) PET / polyvinyl alcohol / ethylene copolymer (Eval) / polyethylene (PE), (5) oriented polypropylene (OP
P) / Eval / PE, (6) Unstretched polypropylene (C
PP) / 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 / P
E, (13) Paper / PE / Al / PE, (14) PET / Al / P
ET / Polypropylene (PP), (15) PET / Al / P
ET / High Density Polyethylene (HDPE), (16) PET /
Al / PE / Low Density Polyethylene (LDPE), (17) Eval / PP, (18) PET / Al / PP, (19) Paper / Al
/ PE, (20) PE / PVDC coated nylon / PE / ethyl vinyl acetate / polyethylene condensate (EV
A), (21) PE / PVDC coated N / PE, (22) EVA
/ PE / Aluminum deposition nylon / PE / EVA (23) Aluminum deposition nylon / N / PE / EVA (24) OPP / PVDC coat 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.

In the present invention, as a method for pre-weighing and dividing and sealing and packaging a predetermined amount of the solid processing agent according to the processing amount of the light-sensitive material to open the package, a seal for packaging the solid processing agent is a preferred embodiment. It is conceivable that the package is opened by making a cut in a part of the package and pulling the package portion not containing the solid processing agent.
As another embodiment, it is possible to open the package by cutting a part of the seal package for solidly packaging the solid processing agent by an external force such as a cutter.

In the present invention, the solid processing agent is preliminarily divided and weighed, and each is packaged in a package in which three or more sides are sealed. Specifically, as a packaging form, a package in which four sides are sealed and a package in which three sides are sealed are packaged. There are forms,
In the case of sealing on four sides, it is common to manufacture by packaging two or more sheets of packaging material, and in the case of a three-way seal, there is a method of manufacturing by sealing three ends, but it is preferable to use a four-way seal. Is more preferably used in the present invention because it can be packaged and the cost can be reduced.

In the present invention, it is most preferable to use gravity as a means for introducing the solid treatment agent packaged in the divided seal package into the treatment tank after opening it by the above method. Compared with the method of charging the solid processing agent into the processing tank by using mechanical power, this means is preferable because the charging section can be made compact and the cost can be reduced.

The supply start signal of the solid processing agent is obtained by detecting the information on the processing amount. Further, the drive means for separating or opening the seal package by the cutting means 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 above-mentioned solid processing agent supplying means has a control means for charging a fixed amount of the solid processing agent according to the processing amount information of the photosensitive 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 component concentration of each processing tank constant and to stabilize the photographic performance.

The processing amount information of the silver halide photographic light-sensitive material means 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 halogen in the processing. It is a value proportional to the processing amount of the silver halide photographic 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 communicated with 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 processing section because there is a certain amount of processing liquid circulation between the processing section and the processing 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 the 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.

Usually, a filter is arranged for the purpose of removing the crystalline foreign matter that is mixed in the processing liquid or is generated by crystallization, and plays a role of removing the foreign matter.

The most preferable method is to put the solid processing agent in a place, such as this auxiliary tank, which communicates with the processing section and in which the temperature is adjusted. 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 and the filtering device, any material used in a general automatic developing machine 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 has a circulation means to dissolve the solid processing agent. The property is also very good.

In the present invention, it is a preferred embodiment that the replenishing water supply means and the replenishing water supply tank are installed (built-in or externally installed) in the automatic developing machine.

The replenishing water supplying means is preferably a processing amount (for example, area) of the photographic material to be processed, an operating time, a temperature controlling time,
The amount of supplementary water added is controlled by information such as the stop time, the environmental temperature and humidity (relative humidity) of the installation location, and the dissolution rate of the solid processing agent.

The replenishing water supply means may be a commonly used bellows pump, and preferably one bellows pump is used to provide a predetermined replenishing water to each processing tank in order to achieve compactness and cost reduction of the automatic processor. Has a distributor capable of supplying.

Next, the replenishing water according to the present invention will be described.

Generally, when the exchange rate in the water replenishment tank is lowered or when the retention time of water becomes long, water scales are generated, and 2-3
There is a problem that water will spoil and produce a foul odor after a week.

When the generated water marks are replenished as they are, they adhere to the surface of the light-sensitive material and cause uneven development in the case of a color developing tank, poor desilvering in the case of a desilvering tank, and stains in the case of a stabilizing tank.
There is a big problem that the product value of the finished product will be significantly reduced even if it is mixed in any tank.

Therefore, in order to remove this water stain, it must be washed regularly, which is very troublesome and cannot be said to be maintenance-free. Further, if it is mixed in the processing tank and cannot be removed by the filter, there is a roller for transportation and the cleaning thereof is a very difficult work.

Therefore, in order to make maintenance free,
The water replenishing tank of the present invention has anti-vibration means.

The anti-vibration means can be achieved by at least one 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 bubbling means These methods will be specifically described.

The chelating agents and bactericides used in the present invention as an anti-vibration means are LEWest "Water Quality Crit".
eria "Phot.Sci. and Eng. vol.9 No.6 398 pages (1965),
MEBeach “Microbiological Gro with in Motion-Pic
ture Processing "SMPTE Journal, vol.85. Mar. (197
6) ， RODeegan, “Photoprocessing Wash Water Bioc
ides "J. Imaging Tech, vol.10, No.6, p. 239 Dec (198
4), JP-A-57-8542, JP-A-58-105145, and JP-A-57-157244
Nos. 62-220951 and the like can be used.

Preferably, the chelating agent is ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetra (methylenephosphonic acid).

[0115]

[Chemical 1]

Preferable examples of the bactericide include phenol compounds, thiazole compounds and benztriazole compounds.

Specific examples include 1,2-benzisothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, 2-octyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-one.
Preferred compounds include isothiazolin-3-one, sodium o-phenylphenol, and benztriazole.

It is preferable that these compounds are in the form of tablets if they are packaged in a package, and if they are divided and weighed in advance, they are individually packaged in the amount to be added at one time. .

As for the method of adding these, the preparer may add them by-hand, but preferably, the solid processing agent supply device of the present invention is installed to add them by-hand, more preferably in the water replenishing tank. It is preferable from the viewpoint of maintenance-free that it is equipped with a vessel and that water is automatically added when water is replenished to a certain amount in the tank.

The method of modifying water with the ion exchange resin of the present invention can be carried out based on the method described in JP-A-61-131632.

As the ion exchange resin, various publicly known cation exchange resins (strongly acidic cation exchange resin, weakly acidic cation exchange resin) and various anion exchange resins (strong bases) described in Kokai Giho, Kogi No. 90-473 and the like are used. Anionic exchange resin), and these can be used alone or in combination. Usually, it is preferable to use a strongly acidic H type cation exchange resin and a weakly basic OH type anion exchange resin. It may be attached to the water replenishment tank, or it may be reformed and brought to another location.

Preferred strong acid cation exchange resins are DIAION SK IB, SK102, SK10.
4, SK106, SK110, SK112, SK116
Mitsubishi Kasei (manufactured) As a preferable OH type strong base anion exchange resin, DI
AION PA406, PA408, PA412, PA
There are 416, PA418, and Mitsubishi Kasei (manufactured by).

The method of irradiating with ultraviolet rays of the present invention is described in
It can be carried out by the method described in 60-263939. As an ultraviolet irradiation device, a product manufactured by Kindai Bio Laboratory (headquarters Kobe City) is small and can be preferably used.

The method of applying the magnetic field of the present invention is described in JP-A-60-2.
It can be carried out by the method described in 63939.

The method of applying ultrasonic waves of the present invention is disclosed in JP-A-60-2.
It can be carried out by the method described in 63940.

The method of applying electrolysis of the present invention is described in JP-A-3-2246.
The method described in No. 81 can be used.

The means for releasing Ag ions of the present invention is
There are a method of putting a silver foil in a water replenishment tank, a method of putting a silver plate, a method of coating the inner wall with silver and a method of adding a silver ion releasing compound.

A preferred silver ion-releasing compound is Biosure SGorSGD (manufactured by Kinki Pipe Giken Co., Ltd.).

Among these anti-vibration means, from the viewpoint of making the apparatus compact, it is preferable. In particular,

[0130]

【Example】

(Embodiment 1) An example of an automatic processor (hereinafter, simply referred to as an automatic processor) to which the present invention can be applied 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 light-sensitive 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. The silver halide photographic light-sensitive material processed by the automatic developing machine according to the present invention is not limited to the exposed photographic paper, and it goes without saying that it may be an exposed negative film or the like. Further, the description of the present invention will be made on a developing machine of substantially three tanks including a color developing tank, a bleach-fixing tank, and a stabilizing tank, but the present invention is not limited to this, and the color developing tank, the bleaching tank, and the fixing tank can be used. The present invention can be applied to an automatic developing machine having substantially four tanks including a tank and a stabilizing tank.

FIG. 2 is a schematic view of a color developing tank 1A which is a processing tank in the II 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, and also brings in components adhering to and adhering to 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 is arranged so as to penetrate the upper wall of the solid processing agent feeding part 11 and be immersed in the processing liquid in the solid processing agent feeding part 11. This heater 7 is used in the processing tank 1
It heats the processing liquid inside, in other words, processing tank 1
Temperature range suitable for processing the processing liquid inside (eg 20-55 ℃)
It is a temperature adjusting means that is held at.

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 processing in this example, but may be after processing or while being immersed in the processing liquid (in such a case, the position where the processing 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, and it is preferable to provide one for each automatic developing machine.

The processing agent supply means 17 for introducing the solid processing agent stored in the cartridge 15 as the storage means into the processing tank is
It is arranged above the filtering section (section) 14.

The tablets 13 stored in the cartridge 15 are shown in FIG.
The seal package which is tightly packaged by the seal package shown in FIG. 1 and which comes out of the cartridge 15 by the opposed roller 17b is cut by the cutter 17a. Due to gravity, the tablets 13 are put into the filtering means (section) 14 from the opened sealed package.

The processing agent supply means 17 is controlled by the processing agent supply control means 9 which will be described later, and in association with the supply signal issued from the processing agent supply control means 9, the tablets 13 are placed in the solid processing agent input section 11. It is supplied to the filtering section (section) 14. In addition,
In the present invention, 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 invention, it is only necessary that the solid processing agent can be dissolved using the processing liquid,
The components according to the processing amount information of the photosensitive material are surely added,
Although it is necessary to keep the processing characteristics of the processing liquid in the processing tank 1 constant, it is more preferable that the solid processing agent is supplied into the circulation path of the processing liquid. Further, the treatment agent supply means 17 is configured so that moisture in the treatment tank of the automatic developing machine or humidity in the outside air, or scattered treatment liquid does 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 that removes not only the tablets 13 but also those derived from the solid processing agent that damage the resulting image when the photosensitive material adheres to the photosensitive material, or cause insufficient processing of the adhered area Is.

The filtering means (section) 14 is made of resin. The filtering means (classification) 14 is a solid processing agent input section.
It is not essential to provide in the inside of 11, and the tablet 13 supplied by the processing agent supplying means 17 may be introduced into the conveying path of the photosensitive material shown in FIG. 1 or the processing liquid in the processing section 2. It is a thing.

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, a processing agent supply 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 replenishment water supply means (a) is a means for replenishing the treatment agent receiving portion 11 with replenishment water (replenishment water) from the replenishment water tank 43 for storing replenishment water, and is a hot water replenishment including a pump, a temperature controller, and the like. It has a device, a solenoid valve, and a rehydration pipe. This replenishing water supply means (a) is for supplementing the water carried out by the photographic material and the water evaporated from the tank surface, while diluting the cumulative inhibitory component eluted by the reaction. 23 in the figure
Indicates evaporative replenishment water setting means.

FIG. 3 is a schematic top view showing the automatic developing machine A of FIG. 1 from above (however, the route is described for the rehydration means for explanation). 32 is a hot water supply device, 33 is a solenoid valve, and 36 is a replenishment pipe. FIG. 4 is a block diagram relating to the control according to this example. FIG. 5 is a block diagram in which a pre-programmed evaporative replenishing 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.

Further, each processing tank 1A, 1B, 1C, 1D,
A replenishing water tank or a replenishing water pump may be provided for each 1E, but if the same replenishing water is used in any tank as the replenishing water to be replenished, and the replenishing water is made into one replenishing water tank, the automatic developing machine becomes compact, and more preferably , Providing only one replenishing water tank and replenishing pump in the automatic machine, and providing a solenoid valve in the replenishing path (pipe etc.) so that each treatment tank can be replenished with the required amount when necessary, or By adjusting the diameter of the pipe for use to adjust the amount of replenishment, only one replenishing water tank 43 and one replenishing water pump can be provided in the automatic developing machine, and the size is further reduced. It should be noted that each of the stabilizing tank 1 is a processing tank.
Regarding C and 1D, it is also possible to omit the replenishing water supply means by supplying the stabilizing solution overflowing from the stabilizing tanks 1D and 1E, respectively. Further, it is preferable that the replenishing water in the replenishing water tank is temperature-controlled.

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 supply means 17. Good.

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. The processing agent supply control means 9 supplies a processing signal to the processing agent supply means 17 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. Emit. Upon receiving the supply signal, the processing agent supply means 17 uses the facing roller 17b to cut the three-way seal package containing the tablets 13 carried from the cartridge 15 into the cutter 17a.
The tablets 13 are cut, and the tablets 13 are supplied to the filtering means (section) 14 in the solid processing agent feeding part 11 by gravity. The supplied tablets 13
It is dissolved by the processing liquid in the solid processing agent input unit 11, but by the processing liquid circulating by the solid processing agent input unit 11 → circulation pump 5 → processing unit 2 → communication window → solid processing agent input unit 11 by the circulation means. Dissolution is accelerated.

At the same time as the above operation, the water replenishment amount setting software 9.23
The replenishing water supply means (a) is provided to supply a signal from the replenishing water to the treatment tank.

On the other hand, the detected light-sensitive material is successively 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 (see the automatic processor A in FIG. 1).

The color developing tank 1A, which is a processing tank,
Bleach-fixing tank 1B, stabilizing tanks 1C, 1D, 1E,
The processing agent supply means 17 may be provided 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.

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 a space for the replenishing tank. Therefore, 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.
The precision of replenishment to the treatment liquid is enhanced, the treatment components to be replenished are not deteriorated, the solid treatment agent is not absorbed, and stable treatment characteristics are obtained.

Although the automatic developing machine 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 confirmed 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 control means are provided for each of the processing tanks.

Example 2 Tables 1, 2 and 3 show the kit forms of conventional treating agents.

[0157]

[Table 1]

[0158]

[Table 2]

In the table, EDTA.Fe salt represents ethylenediaminetetraacetic acid ferric ammonium, and EDTA-4H represents ethylenediaminetetraacetic acid.

[0160]

[Table 3]

The forms of the treating agent of the present invention are shown in Tables 4, 5 and 6.
Shown in.

[0162]

[Table 4]

[0163]

[Table 5]

In the table, EDTA-Fe salt means ferric ammonium salt of ethylenediaminetetraacetic acid.

[0165]

[Table 6]

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

[0167]

[Table 7]

[0168]

[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 chemicals is limited, and water is added in addition to the essential chemical materials.

[0171] Particularly, mixing unnecessarily water means carrying water in the extreme, and the burden on transportation cost becomes large.

In addition, the treating agent of the present invention is solidified and does not require mixing of water at all, so that the treating agent can be in the form of an essential chemical substance. Therefore, Table 1
Comparing No. 3 with Tables 4 to 6, the weight of the replenisher for the same processing amount of the light-sensitive material can be reduced to 46% with the color developing replenisher, 23% with the bleach-fixing replenisher and 23% with 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 constitution as shown in Table 7. .

The conventional processing agent is a minilab quick processing agent which dissolves the processing agent as a replenishing solution and replenishes it according to the processing amount of the photosensitive material. The density difference is gradually increasing.

There is a limit to increase 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 salt. 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.

Further, since the kit parts are constructed in consideration of the storability 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.

Leak the kit solution, put it on your clothes,
If it gets on your skin, an unexpected accident will 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. .

Also, when transporting the processing agent, it is subject to legal restrictions.

That is, it is stipulated by UN (United Nations) rules and the like, 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 replenisher, it can be directly replenished to the tank solution according to the processing amount of the photosensitive material. Only by increasing the ratio of the consuming component, an advantageous constitution which is not limited to the solubility can be taken, so that there is no fear of material precipitation problems.

Further, since the kit form is not 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 A
After imagewise exposing 5 (manufactured by Konica Corp.), Konica Big Mini Lab BM-101 (manufactured by Konica Corp.) was modified to the treatment agent supplying method shown in FIG. The continuous treatment was carried out by remodeling so that the treatment process described above was performed. However, the system for controlling the supply of replenishment water was the same as in Example 1.

[0184]

[Table 9]

Stable was the countercurrent system from 3 to 1, and the overflow liquid of stable-1 was entirely introduced into the bleach-fixing tank. The carryover per 1 m ^{2 of} the light-sensitive material was 50 ml / m ² in all tanks.

Evaporation correction is carried out at the time of temperature control at color development, bleach-fixing, and stability of 9.0 ml / hour, 7.2 ml / hour, 14.1 ml / hour for each hour, and when temperature control is not performed. , 3.8m each
L / hour, 3.1 ml / hour, and 6.1 ml / hour were integrated, and the temperature control was started at the same time.

At the start, the tank liquid is Konica Color Q
A paper color development starter 82P-1B, (Konica Color QA paper bleach-fix starter 82P-2B manufactured by Konica Corporation)
(Same as above), Konica Color QA Paper Stable Starter 82P
-3B (same as above).

Treated tablets for color paper were prepared according to the following operations (A to G).

1) Tablet 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 Tablet A for color development replenishment for individual color paper
The agent was created.

Procedure (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 obtained mixture was mixed with a tableting machine modified from Tough Pressed Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd.
Compressing tableting was carried out with the filling amount per tablet being 1.0 g to prepare 100 tablet B agents for color developing replenishment for color paper.

Operation (C) 30.0 g of Tinopearl SFP (manufactured by Ciba Geigy), 3.7 g of sodium sulfite, 0.3 g of potassium bromide, 25 g of diethylenetriamine-5-acetic acid, and 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 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 1.0 g, and the mixture was compressed into 100 tablets.
Individual tablets C for color development replenishment 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 the obtained mixture was manufactured by Kikusui Seisakusho Co., Ltd. Tough Pressed Collect 1527H.
A tableting machine prepared by modifying U was used to perform compression tableting with a filling amount of 3.0 g per tablet to prepare 110 tablet D agents for color development replenishment for color paper.

2) Bleach-fixing replenishing tablet for color paper Operation (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) 1640 g of ammonium thiosulfate, 750 g of sodium sulfite,
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 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 13.4 g.
A bleach-fixing replenishing tablet B agent for color paper was prepared.

3) Tablet for stable replenishment for color paper (G) Sodium carbonate monohydrate 10 g, 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 per tablet was 3.1 g and the mixture was compressed to 360
Individual stable refill tablets for color paper were prepared.

As for the above-mentioned tablets for color development replenishment, one tablet for each of the agents A, B, C and D, for a total of four tablets, was 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. Furthermore, regarding tablets for stable replenishment,
Each tablet was packaged in 1 packet and packaged in the same manner as above.

As the seal packing material, a polyethylene terephthalate four-way seal packing having a thickness of 0.1 mm was adopted.

As a comparative example, the present tablet and the replenishing water corresponding thereto were placed in a replenishing tank, and a replenishing solution for 10 l was prepared and used.

However, the evaporation correction in the comparison process was performed with the replenisher.

Further, as a comparative example, the above (A) to
The tablet of (G) is wrapped with the PTP packaging material shown in FIG.
The method shown in FIG. 12 was changed to a processing agent supply means for pushing out the tablets in the PTP package.

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 sample exposed to wedge was developed. The maximum reflection density of blue was measured.

However, the color developing agent in the color developing agent is
When the replenishment rate is 50 ml / m ² , 1.2 times 25 ml / m ² is 1.45 times, 150 ml / m
^{In 2} , the value was changed to 0.9 times, and the amount of consumption was corrected.

The amount of maleic acid in the bleach-fixing solution is
At the time of lowering the replenishment rate, the amount was increased by the amount corresponding to the increase in pH due to the mixing of the color developing solution. Table 10 shows a comparative example of each method.

[0204]

[Table 10]

Further, the replenishing amount of the replenishing solution and the renewal rate were changed, continuous processing was performed, the solid processing agent charging method of the present invention was compared with the comparative example method, and the concentration of the bleach-fixing solution was measured. The concentration rate was determined by measuring the iron ion concentration in the tank solution by atomic absorption.

Further, it was dissolved in a color developing agent to observe the dissolved state when a replenisher was prepared.

[0207]

[Table 11]

As is apparent from Table 11 above, in the conventional replenisher preparation method, when the replenisher was made low, the replenisher had to be thickened, and when the replenisher was prepared, it was not completely dissolved and insoluble matter remained. I will end up. 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. Further, in the case of the comparative example, it was found that the bleach-fixing solution did not sulfurize, but malfunctions during tablet extrusion were likely to occur, and as a result, processing stability was lower than in the present invention.

On the other hand, in the direct charging method of the present invention,
Since no replenisher is prepared, neither dissolution nor deterioration of processability occurs.

Further, in the case of the bleach-fixing solution, it was found that the replenishing solution at the time of low replenishing has a low pH and thus has poor storability, and is sulfided in a few weeks. However, according to the method of the present invention, since it is not necessary to prepare a replenishing solution, the sulfurization of the bleach-fixing solution does not occur at all.

Further, in the comparative example system, the concentration ratio of the bleach-fixing solution increases, whereas in the system of the present invention, the solution concentration hardly occurs.

Example 4 Konica QA Paper Type-
After image-wise exposing 5 (manufactured by Konica Corporation), a modified NPS-808 machine (manufactured by Konica Corporation) having the configuration shown in FIG.
Was treated according to the following treatment steps. However, the replenishing water in the replenishing water 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 developing machine was 27 ° C. and 60% RH, and the replenishing water was replenished when the amount of evaporation reached 100 ml.

The formula (1) of Japanese Patent Laid-Open No. 3-280042 was used for the method of calculating the supplementary water. The processed light-sensitive material was processed at 2.0 m ² per day and continuously processed for 2 months.

The composition of the processing liquid is shown below.

(Color developer) Potassium bromide 0.02g Potassium chloride 3.2g Potassium carbonate 30g Potassium sulfite 0.2g Sodium diethylenetriamine pentaacetate 2g Sodium nitrilotrimethylenephosphonate 2g Tinopearl SFP 2g Disodium-N, N-bis (sulfonate ethyl) ) Hydroxylamine 5g 4-Amino-3-methyl-N-ethyl N- [β- (methanesulfonamido) ethyl] aniline sulfate 7g (CD-3) Water was added to adjust the pH to 10.10.

(Bleaching Fixing Solution) Diethylenetriaminepentaacetic acid ferric ammonium 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 adjust the pH to 7.0.

(Stabilizer) Water 800 g 1,2-Benzisothiazolin-3-one 0.1 g 1-Hydroxyethylidene-1,1-diphosphonic acid 5.0 g Ethylenediaminetetraacetic acid 1.0 g Tinopearl SFP (manufactured by Ciba Geigy) 2.0 g Ammonium sulfate 2.5 g 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 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 by 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.

For comparison, a running test was also conducted on a color developing tank, a bleach-fixing tank, and a stabilizing tank, which were filled with water up to the overflow port once every morning every evening.

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 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 1.0 g, and the mixture was compressed into 100 tablets.
Individual tablets C for color development replenishment for color paper were prepared.

Operation (D) 350 g of potassium carbonate is ground 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 the obtained mixture was manufactured by Kikusui Seisakusho Co., Ltd. Tough Pressed Collect 1527H.
A tableting machine prepared by modifying U was used to perform compression tableting 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 replenishing tablet for color paper Operation (E) Ethylenediaminetetraferric acetate 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 toughly pressed by Kikusui Seisakusho Co., Ltd. 15
The filling amount per tablet was 8.
Tablet compression was performed with 6 g to prepare 170 tablets of bleach-fixing replenishing tablet A for color paper.

Operation (F) 1640 g of ammonium thiosulfate, 750 g of sodium sulfite,
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 with a tableting machine 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 10 g, 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. .

The above-mentioned replenishing tablets for color paper are shown in Table 7.
And each tablet is sealed on four sides using a laminated polymer resin film made of PET / polyvinyl alcohol / ethylene copolymer / polyethylene so that the amount shown in Table 8 is obtained, and further tableting for each part of each replenisher. Then, the total amount was adjusted to the amount shown in Table 2 so that the composition ratio was the same as that of one tablet, and four-way sealing was performed in the same manner 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 Sodium diethylenetriamine pentaacetate 2g Sodium nitrilotrimethylenephosphonate 2g Tinopearl SFP 2g Disodium-N, N-bis (sulfonate ethyl) ) Hydroxylamine 5g 4-Amino-3-methyl-N-ethyl N- [β- (methanesulfonamido) ethyl] aniline sulfate 7g (CD-3) Water was added to adjust the pH to 10.10.

(Bleach-fixing solution) Diethylenetriaminepentaacetic acid ferric ammonium 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 800 g 1,2-Benzisothiazolin-3-one 0.1 g 1-Hydroxyethylidene-1,1-diphosphonic acid 5.0 g Ethylenediaminetetraacetic acid 1.0 g Chinopearl SFP (Ciba Geigy) 2.0 g Ammonium sulfate 2.5 g 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 pH was adjusted to 8.0 with 50% sulfuric acid or 25% aqueous ammonia.

[0237] The running experiment was performed by continuously processing 50 24EXP color films per hour for 3 hours.
750 sheets) were processed and the tablet solubility, photographic performance, handleability, etc. at that time were evaluated.

Table 12 shows the amount of tablets and the amount of supplementary water.

[0239]

[Table 12]

[0240] color developing replenisher tablet when timing tablets and the replenishing water to enter the color paper is 1 m ² processed 7.85
For g, 80 ml of replenishing water, 39.7 g of bleach-fixing replenisher tablets, 200 ml of replenishing water, 2.6 g of stable replenishing tablets, 2 replenishing water
It is replenished with 50 ml. Based on this amount, the addition time (Table 12) was changed depending on the tablet amount, and 80 ml, 200 ml, and 250 ml of replenishing water were supplied when the tablet amount was reached.

[0241]

[Table 13]

As a result, in view of workability of exchanging tablet cartridges, adhesion of tablets to packaging materials, solubility of tablets, and process stability, all replenishers are solidified and replenished separately from replenishing water. In some cases, it was also found that 0.5 g to 30 g was particularly good.

Example 6 A fixing tablet was prepared according to the following procedure.

2500 g of ammonium thiosulfate, 150 g of sodium sulfite, 150 g of potassium carbonate and 20 g of ethylenediaminetetraacetic acid disodium salt are pulverized and granulated. The amount of water sprayed is 30 ml, and after granulation, it is dried at 60 ° C for 60 minutes. Next, the granulated product is dried in vacuum at 40 ° C. for 8 hours to almost completely remove the water content of the granulated product.

[0245] 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 Pressed Collect 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, 10 liters of a fixer having the following formulation was prepared.

[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. 6 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 in the temperature control unit as shown in the table below.
The remaining state of the tablets in the auxiliary tank when the individual pieces were added was observed.

For comparison, the dissolution test unit (B) shown in FIG. 7 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.

[0250]

[Table 14]

[0251]

[Table 15]

In this experiment, 60 hours per hour were measured by an automatic processor.
This is a high-speed dissolution experiment assuming replenishment equivalent to this, and evaluation was performed using a fixing agent with the highest dissolution frequency.

As is apparent from Table 14 above, in the method of directly adding the processing agent to the processing solution, which is the dissolution method of the present invention, the temperature of the processing tank can be dissolved at 25 ° C. or higher without leaving any insoluble matter. The temperature can control the dissolution speed.

At 20 ° C., a small amount of insoluble matter remained, but there was practically no problem.

Further, as in the case of the unit (B) shown in FIG. 7, in the method of once dissolving with the replenishing liquid preparation filter, it did not dissolve within the specified time, so all were clogged in the filter and it was inoperable.

Assuming that the 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 7 Konica Color Super DD-
After image-wise exposing 100 films, the color negative film processor CL-KP-50QA was modified into the system shown in FIG. 19 and subjected to continuous processing.

Fixing is from 2 to 1, stability is from 3 to 2,2
It was a countercurrent method from 1 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- during color adjustment.
10ml, 6.5ml, 7ml, 7ml, 8.6ml in 1 hour each in 3 tanks
Evaporation correction was performed using a program that replenishes 8.6 and 9.3 ml of water. When not in operation, the non-operation time is added up, and color development, bleaching, fixing-1, fixing-2, stable-1, stable-2,
Stable -3 with evaporation-corrected water 7.5 ml, 5 m per hour each
The amounts of 1, 6 ml, 6 ml, 5 ml, 5 ml and 5 ml were collectively 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.

Colored negative film treated tablets were 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 was added to a commercially available Bandham mill. Grind 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 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 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 1.1 g, and 126 tablets of color development supplement A for 126 color negatives were developed. It was created.

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 the 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, in the same manner as in the operation (1), compression tableting was performed 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, in the same manner as in the operation (1), compression tableting was performed with a tableting machine at a filling amount of 3.9 g per tablet to prepare 120 color developing agent replenishing tablet C agents for color negative.

2) Bleaching Replenishing Tablet for Color Negative Operation (4) 1,3-Propanediamine 4 ferric ammonium acetate 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) 133 g of succinic acid, 200 g of 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) In the same manner as in the operation (1), 66.7 g of potassium sulfate, 60 g of potassium hydrogen carbonate and 8 g of mannite are pulverized, mixed and granulated. 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 granulated product prepared in the above operations (4)-(6) was used 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 was compressed into tablets using a tableting machine modified from Tough Pressed Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd. with a filling amount of 6.5 g per tablet to prepare 80 bleaching tablets for color negative bleaching. .

3) Fixing replenishing tablet 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 color negative fixing replenishing tablets were prepared. .

4) Stable replenishing tablet for color negative (10) m-hydroxybenzaldehyde 150 g, sodium lauryl sulfate 20 g, ethylenediamine tetrasodium acetate 60 g,
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) The granules prepared in the above operation (10) were placed in a room where the humidity was adjusted to 25 ° C. and 40% RH or less by a tableting machine which was modified from Kikusui Mfg. Co., Ltd.'s Tough Press To Correct 1527HU. Compressing tableting was carried out with the filling amount per tablet being 0.48 g, to prepare 280 stable supplement tablets for color negative.

Next, the above-mentioned tablets are 2 tablets, 1 tablet and 1 tablet each of A, B and C for the color development replenishing tablet, 2 tablets for the bleach replenishing tablet, 3 tablets for the fixing replenishing tablet, respectively.
As for tablets for stable replenishment, one tablet was made into one packet, and continuous 20-minute packages were each sealed and packaged, and a polyethylene terephthalate film having a thickness of 0.1 mm was packaged by a four-way sealing method. The same packaging material as that used in Example 3 was used.

The timing of replenishing the tablets and the supplementary water was as shown in Table 15 above.

The processing was carried out so that the overflow from the color developing tank was 5% of the tank solution per day.

Further, as a comparative example, the tablets and makeup water were dissolved in a supplement tank for 10 l and supplemented from the supplement tank. At this time, replenishment was carried out so that the amount was the same as in the case of the tablets.

As a comparative example, the color negative tablet treating agent was packaged in the PTP shown in FIG. 12, and the treatment agent supplying means for pushing out the tablets in the PTP package was changed by the method shown in FIG.

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 16.

[0279]

[Table 16]

As is clear from Table 16 above, in the comparative method until such processing, deterioration of the color developing solution occurred and the photographic density was lowered, but in comparison with the method of the present invention, it was completely You can see that it does not change.

Further, 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 8) (1) Ethylenediaminetetraacetic acid was added to the hot water supply device 32 of FIG. (2) 1,2-benzisothiazolin-3-one was added at 0.1 g / l (3) 5-chloro-2-methyl-4-isothiazolin-3-one was added
0.1g / l addition (4) Diaion SKIB (strong acid cation exchange resin, Mitsubishi Kasei) and Diaion PA406 (OH type strong base anion exchange resin, Mitsubishi Kasei) volume ratio 1: 1
(5) Use UV irradiation device (Kindai Bio Lab.) (6) Biosure SGD (Kinki Pipe Giken) 1 g /
1 addition (7) The same experiment as in Example 3 was carried out without using any antifungal means. The results were exactly the same except for (7). Furthermore, the state in the refill water tank was visually observed.

The results are good except for (7),
In (7), something like "mo" was generated on the surface and the wall.

(7) is because development unevenness, desilvering unevenness, and stains are severe, and the suspended matter in the replenishing water tank enters each processing tank and adheres to the photosensitive material.

Example 9 Next, five comparative examples and another example of the present invention will be described. 8 to 12 show a supply device of a comparative example.

FIG. 8 shows Comparative Example 1, FIG. 8 (A) is a sectional view of the powdery processing agent supplying device, and FIG. 8 (B) is a perspective view of the package. The supply device 50 is composed of a hopper or package 51 for storing the powdery treatment agent, a measuring hole 53 for measuring the powdery treatment agent, and a rotary drum 52 for feeding 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. At that time, fine powder flew and the workability was poor. A certain amount of powdered chemical is measured in the measuring hole 53, and when the drum 52 is rotated by the command of the processing amount detecting means of the photosensitive material and is in communication with the discharge part 56, it stops and passes through the discharge part 56, and a fixed amount of powdery chemicals. Is supplied to the constant temperature section (filter tank) of the automatic processor. 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. A running test was carried out in the same manner with this feeder attached to the automatic developing machine, but the particle size distribution of the part where moisture absorption was insufficient and the powdered chemical was not absorbed in the package 51 and the part where it was not so changed due to insufficient moisture resistance. The amount of powdered chemical remaining in the hopper 51 changed the amount entering the measuring hole 53 due to the weight of the chemical, and the quantification accuracy deviated, so that stable photographic performance could not be obtained. In some cases, powdery chemicals hardened and did not enter the measuring holes 53. Furthermore, depending on the size of the powdered chemical, fine powder moves downward, and powder with a large proportion rises upward, which has the drawback that the components are balanced. In addition, there is a drawback that fine powder does not rotate properly because it enters the gap of the drum, so it is not maintenance-free.

[0287] Fig. 9 is a perspective view of another powdery processing agent supply device showing comparative example 2.

The powder supply chemical storage unit 63 of the supply device 60 is divided into a plurality of parts, 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.

According to the processing information of the photosensitive material, the rotating body 67 quantitatively transfers the powdery processing agent received on the table 66 to the discharging section 68 for each component and supplies it.

When a running experiment was carried out using this feeder, there was a problem exactly the same as in Comparative Example 1.

That is, there is a problem in workability due to fine powder when the powdery processing agent is put into the hopper 64, and a problem of quantitative accuracy.
It is true that the dehumidifying device and the parts are divided, so that the storage stability is good, but caking in the storage part is still present.

Further, there is a big problem in the 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. 10 is a cross-sectional view showing still another supply device of the powdery treatment agent showing Comparative Example 3.

In the supplying device 70, the powdery processing agent is put into the hopper 71, and the piston 75 moves in the horizontal direction (to the right) according to the processing amount of the photosensitive material, and a fixed amount of the powdery agent enters the measuring hole 72 and the piston 75.
Moves in the opposite horizontal direction (to the left), and the discharging unit 74 supplies the quantitative powdered material to a constant temperature tank (filter tank).

When a running experiment was carried out using this feeder, there was a problem exactly the same as in Comparative Example 1.

FIG. 11 is a cross-sectional view showing still another supply device for the powdery treatment agent showing Comparative Example 4.

The supply device 80 has a function of entering (loading) the package 81 into the powdery treatment agent 88 and automatically opening it by the roller 83, and controlling the rotation speed of the screw 82 to discharge the powdery chemicals. It is a device supplied by 84.

Since it has a function of automatically opening the package, fine powder does not fly at the time of opening and mounting, which is good. However, since powder chemicals are divided and weighed according to the amount of processed photosensitive material, the same as in Comparative 1 It turned out that there was a problem. In particular, this method has a drawback that the quantitative accuracy depends on the size of the pitch (peak / valley) of the screw, and fine powder having a small amount of accuracy is preferentially discharged. In addition, the powder attached to the screw is damaged by humidity, the rotation of the screw becomes dull, and the quantification accuracy is further reduced.

Also, the maintainability is poor.

FIG. 12 shows PTP (Pressure Throu
gh Package) Regarding the device for feeding the packed solid processing agent,
(A) is a cross-sectional view of the treating 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
Sectional drawing which shows the loading state of the solid processing agent packed by PTP.

The processing agent storage container contains the PTP-packed solid processing agent, and may be stored individually in the 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 packaged in the form of tablets.

The solid processing agent packaged in PTP is supplied from below the storage container, and when a certain amount of the photosensitive material is processed, the information of the processing amount detection means is sent to the processing agent supply control means and the solid processing agent packaged in PTP by the motor. The lower part of the PTP package (mainly made of aluminum) is peeled off by pushing the processing agent onto a wedge-shaped fixing plate and crushing it, and the solid processing agent is put into the processing tank from the inlet. The empty PTP package after being thrown in is further pushed out and discarded from the waste port. This method, compared with the method shown in FIGS. 10 to 13, the solid processing agent is divided and weighed in advance, so the quantification accuracy is improved,
Since the empty PTP package after loading is bulky, waste is bulky, which is not preferable. Further, when the solid processing agent is squeezed out by crushing the PTP, there may be a case where a malfunction occurs depending on how the aluminum seal is shaken or undesired. Furthermore, since PTP uses an aluminum sealant, the cost is high, which is not preferable.

Next, specific examples of packaging of four-way seals and three-way seals according to the present invention are shown in FIGS. However, the present invention is not limited to these.

In the sealed packaging shown in FIG. 13 (A), several kinds of tablets are contained in one packaging unit. Figure 13 (B)
Are packed with tablets of different kinds and sizes. Figure 13
(C) is a package of granules or powder. Figure 13
(D) contains one of the same size. Figure
In 13 (E), a plurality of the same chemicals of the same size are contained as small tablets.

For other patterns as well, FIG.
It shows in (X).

FIGS. 14A, 14B and 14C are plan views showing an example of a four-way seal. FIG. 14 (D) shows an example of a three-way seal.

FIG. 15 is a cross-sectional view showing a state in which tablets, granules or powders are 43-sealed and heat-sealed, and then folded and stored in a container.

Further, FIGS. 16 (a) and (b) and FIGS. 17 (a) and (b)
Another embodiment of FIGS. 18, 19, and 20 will be described.

FIGS. 16 (a) and 16 (b) show a "U-shaped" half punching system.

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 to cause the solid processing agent 13 to rotate. The packed body 801 shown in 32 (a) is moved to a position as shown in FIG. 16 (a) and stopped. Package 80
The method of moving 1 is a method of detecting a notch previously provided in the packaging body 801, a detection of a printed pattern or an eye mark, a packaging body.
Any method such as the detection of the treatment agent 10 of 801 may be used, but the essential point is to detect the required number of solid treatment agents 13 with high accuracy. Next in Figure 16
As shown in (b), the punch male mold 300 moves downward to cut the package 801 and the solid processing agent 13 is introduced into the processing tank of the automatic processor through the input port 901 in FIG. 17 (a). The cut end cut by the punch male die 300 is a punch shape 601 as shown in FIG. 17 (b).
It becomes a U-shaped like.

In the case of such a system, the solid processing agent 13 may be any of powder, granules and tablets, but it is preferable to use a punch male type tablet in which chemicals are not easily attached. Further, the tablets 13 do not adhere to the package so much that stains are less likely to occur, and are safe for the user to handle. Used packaging 801 is waste box 1
It is possible to enter 02 and dispose of them all together. This waste box 10
For item 2, it is preferable to reuse the used package storage box 701.

18 and 19 show a method of cutting off 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 carrying roller 201 is rotated to cause the solid processing agent 13 to rotate. The solid processing agent 13 moves the packed package 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.

As a method of moving the package, any method such as detecting a notch provided in the package 11 in advance, detecting a print pattern, detecting the treatment of the package, or the like is essential. It should be detected with high accuracy. Next, the ceramic cutter 201 cuts the package 11. When the cutting is completed, the ironing roller 401 and the conveyance roller 501 are rotated and the solid processing agent
13 The iron 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 enters the waste box 602. The waste box 602 is preferably a reused box for a used package.

In the case of such a system, the solid processing agent 13 may be any of powder, granules and tablets, but it is preferable to use tablets in which chemicals do not adhere 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.

The used packages 11 can be put together in a waste box 602 and discarded.

FIGS. 20 (a) and 20 (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 is rotated, and at the same time, a circle made of ceramic or stainless steel is used. The blade 301 rotates and the lower part of the continuous package 603 is cut into two parts, and the solid processing agent 1
Turn on 3. The repackaging body 603 divided into two is spread by suction on the suction guide 202 on both sides, and the solid processing agent 13 inside is easily dropped. The empty package 603 without the solid processing 10 is moved by the transport roller 401 when the next solid processing agent 13 is input, and is discarded into the package storage box 101.

In addition to the above-mentioned method, this halving may be made by attaching a notch or the like to the continuous package and tearing it while winding it with a roller.

In the case of such a system, the solid processing agent 13 may be any of powder, granules and tablets, but tablets having no chemicals attached to the punch male die are preferred. Further, the tablet does not adhere to the seal of the package so much that the stain is less likely to occur.

The used packaging body 603 can be disposed of together in the packaging body storage box 101 and discarded.

[0322]

As described above, in the automatic developing machine for silver halide photographic light-sensitive material of the present invention, the solid processing agents preliminarily divided and weighed are sealed in three or more sides, and after opening, they are directly added to the processing tank. Then, the photographic performance can be made uniform by supplementing the components that are insufficient or dissolved depending on the photographic material and replenishing supplementary water separately in the required amount.

In the present invention, the front and rear solid processing agents are packaged in three or more side seal packages, so that the solid processing agents are moisture-proof.

The conventional replenishing solution preparation work by the user is no longer necessary, and the processing solution can be automatically added according to the processing amount of the photographic material simply by setting the solid processing agent in advance. The performance of is maintained constant.

The volume of the replenishment tank 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.

Further, the replenishers in the low replenishment era were all made thicker by using the performance up to the solubility limit of chemicals, and all the replenishers had a concentration 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 can be seen 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 to reach a high concentration beyond the processing solution used.

For the above reason, the conventional replenishment method cannot reduce the replenishment rate because the replenisher cannot be further concentrated due to the 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 method of the present invention. Become. Further, both are achieved and realized by the replenishment method 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 of being difficult to dissolve solid processing agents, but recently, most of them have been liquid-typed 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 the solid processing agent, which was divided and weighed in small amounts, directly into the processing solution tank whose temperature was controlled to a constant temperature, and thus stable without any problem even if dissolved over time. It was discovered that replenishment work for maintaining the photographic performance can be performed. That is, a replenisher kit which has been conventionally considered to be required to store a replenisher that has been completely dissolved in a replenisher tank and to inject it into a treatment tank as needed to maintain the components is a silver halide according to the present invention. The solid processing agent, which is divided and weighed in advance according to the processing amount information of the photographic light-sensitive material, is periodically added to at least a part of the processing tank whose temperature is adjusted to a constant temperature, and replenishing water is added to the same processing tank as necessary. By periodically supplying a fixed amount to a part, the complicated work of dissolving the chemical replenisher by the user is eliminated, the automatic developer replenishment tank is eliminated, and the dangerous concentrated liquid chemical kit and the conventional chemical bottle containing it are eliminated. In addition, since there is no replenishing tank, there is no replenishing solution and the life time of the solution is significantly improved, and the processing stability can be dramatically improved. In addition, a system has always been adopted in which the replenisher is always dissolved before use.
There is also a method of replenishing the ABC3 package of the concentrated liquid kit called R replenishment and the replenishment water by directly collecting the replenishment water with a bellows metering pump, but it is not directly input to the treatment tank separately but four components are mixed in advance. However, consideration has been given to adding it, 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 plan view of the automatic processor.

FIG. 4 is a block diagram including control means of the automatic processor.

FIG. 5 is a block diagram in which a melting table of control means is added.

FIG. 6 is a configuration diagram of a dissolution test unit.

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

FIG. 8 is a cross-sectional view of a powdery processing agent supply device of a comparative example and a perspective view of a package.

FIG. 9 is a perspective view of a powdery processing agent supply device.

FIG. 10 is a cross-sectional view of another powdery processing agent supply device.

FIG. 11 is a cross-sectional view showing another embodiment of the powdery treatment agent supply device.

FIG. 12 is a sectional view and a perspective view of a PTP packaging treatment agent supply device according to the present invention.

FIG. 13 is a plan view of the seal packaging.

FIG. 14 is a plan view showing a specific example of a three-sided and four-sided seal packaging.

FIG. 15 is a diagram showing a state in which a solid processing agent sealed and packaged is contained in a container.

FIG. 16 is a device for cutting a package by cutting it into a U-shape.

FIG. 17 is a perspective view of a device for half-drawing the package of FIG. 31 into a U-shape.

FIG. 18 is an apparatus showing a method of cutting off a package.

FIG. 19 is a perspective view of the device showing the cutting method of FIG. 33.

FIG. 20 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 (solid processing agent) 14 Filtration part (classification) 14A Stirring blade 14B Stirring blade 14C Shear gear 14D Vibrator 14E Magnetic rotating blade 14F Rotating magnet body 14L Transmission mechanism 14M Motor 14N Partition member 14P Injection pump 15 Cartridge 16 Lead wire 17 Processing agent supply means 17 'Processing agent supply section 18 Push claw 19 Cam 19' Pinion gear 21 Tablet pressing spring 23 Pre-programmed evaporative rehydration setting means 24 Tablet stopper 25 Screw 27 Screw 28 Container 29 Processing agent guide section 32 Hot water replenishment device 33 Solenoid valve 35 Drying part 36 Replenishment pipe 41 Pipe (for replenishment water) 42 Replenishment water supply means 43 Replenishment tank

Claims (7)

[Claims] 1. At least one processing tank containing a processing solution for processing an exposed silver halide photosensitive material, a processing agent charging section through which this processing tank and the processing solution flow, and divided and weighed in advance to a fixed amount. A storage means for storing a solid processing agent sealed in three or more sides, a supplying means for charging the solid processing agent, a processing amount detecting means for detecting processing information of the silver halide photographic light-sensitive material, and the detection Control means for actuating the supply means in response to information on the amount of processing of the silver halide photographic light-sensitive material detected by the means, and supplying the solid processing agent. An automatic developing machine for silver halide photographic light-sensitive materials, which comprises adding a solid processing agent after opening the material. 2. The automatic developing machine for silver halide photographic light-sensitive materials according to claim 1, wherein the processing agent supply means charges the solid processing agent by gravity after opening the seal packaging material. 3. The solid processing agent is introduced by the processing agent supplying means by cutting or cutting a part of the seal packaging material.
2. An automatic developing machine for silver halide photographic light-sensitive materials as described in 2. 4. The amount of solid processing agent added at one time is 0.1 g
The automatic developing machine for silver halide photographic light-sensitive materials according to claim 1, wherein the automatic developing machine has a weight of 50 g. 5. The automatic developing machine for silver halide photographic light-sensitive materials according to claim 2, wherein the solid processing agent is a granular or tablet-formed tablet formed by a granulation step. 6. A processing tank to which the solid processing agent is supplied communicates with a processing section for processing the silver halide photosensitive material and a processing section for charging and dissolving the solid processing agent. 2. An automatic developing machine for silver halide photographic light-sensitive materials according to claim 1, further comprising a circulation means for circulating a processing liquid between the processing section and the processing agent feeding section. 7. A silver halide photograph according to claim 1, further comprising a replenishing water supply means for replenishing replenishing water to said processing tank, the operation of which is controlled in accordance with processing amount information of said photographic light-sensitive material. Automatic developing machine for photosensitive materials.