JP3136383B2 - Automatic developing machine for silver halide photographic materials - Google Patents

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 a silver halide photographic light-sensitive material (hereinafter sometimes simply referred to as an automatic developing machine). The present invention relates to an automatic processor in which the width is improved in workability and the stability of chemicals is dramatically improved.

[0002]

2. Description of the Related Art Silver halide color photographic materials (hereinafter, sometimes referred to as photographic materials or photographic materials) are
After exposure, the film is processed by processes such as development, desilvering, washing, and stabilization. The black-and-white silver halide photographic material is developed and fixed after exposure. Black and white developer, color developer, bleaching solution, bleach-fixing solution for desilvering process, fixing solution for fixing process, tap water or ion exchange water for washing, stabilizing solution for anhydrous washing, and dye stabilization A stabilizing solution is used for each treatment.

A liquid having a processing function for performing each of these processing steps is called a processing liquid. Each processing solution is usually 30 ~
The temperature is adjusted to 40 ° C., and the photographic material is immersed in these processing solutions for processing.

[0004] Such processing is usually carried out by sequentially transporting the processing solution in a processing tank containing the processing solution by an automatic developing machine (hereinafter referred to as an automatic developing machine) or the like.

When an automatic developing machine is used, it has a developing section, a fixing section, a desilvering section, a washing or stabilizing section, and a drying section. It generally refers to a developing machine having means.

[0006] In the case of processing by such an automatic developing machine, a method of replenishing a processing agent in order to keep the activity of a processing solution in a processing tank constant has been widely adopted.

As this processing agent replenishment method, a method in which a replenisher in which a processing agent is dissolved is prepared in advance is widely used.

Specifically, the processing operation is performed while a replenisher prepared in advance is supplied from the replenishing tank into the processing tank at an appropriate time.

In this case, the replenisher itself stored in the replenishment tank is generally prepared and adjusted in another place. However, in a minilab or the like, a fixed amount of replenisher is provided in a replenishment tank installed close to the developing machine. Usually, they are adjusted at once, but they have been prepared by manual dissolution or dissolution mixing by a mixer.

That is, a processing agent for a silver halide photographic light-sensitive material (hereinafter sometimes referred to as a photographic processing agent) is commercially available in powder or liquid form.
In the case of powder, the solution is prepared by manually dissolving it in a certain amount of water. In the case of a powder, the solution is also concentrated.

The replenishment tank may be installed beside the automatic machine, and it is necessary to secure a considerable space. In the minilabs, which have been increasing rapidly in recent years, the replenishment tank is built in the body of the automatic machine.
It is necessary for each of the liquids L, and it is necessary to secure a space for the replenishment tank.

Replenishing processing agents are divided into several parts in order to obtain good and stable performance in 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 part of ferric salt of an organic acid as an oxidizing agent and a part of thiosulfuric acid as a reducing agent. When a replenisher is prepared, the concentrated part of the ferric organic acid and the thiosulfate-containing part are mixed together, and a certain amount of water is added for use.

The above-mentioned concentrated parts are put in a container such as a plastic container, and these are put together and put in an outer bag (for example, a cardboard box) to be marketed as one unit.

The replenishing agent prepared by dissolving, diluting and mixing the above-mentioned parts is used after finishing in a fixed amount. However, the replenishing agent has the following disadvantages.

First, most of the conventional kits are concentrated aqueous solutions which are concentrated to improve workability. Most of them are extremely dangerous aqueous solutions having a pH of 2.0 or lower or 12.0 or higher. It is often dangerous and is also a strong oxidizing or reducing agent, making it extremely corrosive to transport by ship or aircraft. Also, since it is an aqueous solution, its solubility is limited and its weight and volume are larger than those of a solid. As described above, since the concentrate is a dangerous substance, the container must be destroyed even if dropped from a certain height and must not be spilled because the container is more robust. Is in question.

Second, each part is put in a container,
Depending on the replenishing agent, the number of parts is several, and the number of containers is considerably large for each unit, and a large amount of space is required 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 l is 1 unit and 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. Each of A, B and C is contained in a 500 ml plastic container. Similarly, the bleach-fix solution is divided into three bottles with 8 l as one unit, and the stabilizer is divided into two bottles with 10 l as one unit. Each of these replenishers will be stored and transported in outer boxes of various sizes, but the outer box is a small stable solution of about 17 cm × 14 cm
Approximately 18.5cm x 30.5cm with a relatively large bleach-fixing agent at 16.5cm
It measures 22.5cm and can only be stacked with the same type of replenisher in storage, transport or in stores, and eventually requires a lot of space.

A 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 disposal of plastic containers has become a problem particularly in photography. Photo plastic containers are low in cost, convenient for storage and transportation, and have excellent chemical resistance, but plastic containers have little biodegradability,
If accumulated and incinerated, a large amount of carbon dioxide gas is generated, which contributes to global warming and acid rain, and users have a problem in that a large amount of plastic containers are piled up in a narrow work space. In addition, it has been pointed out that it cannot be crushed due to its high strength and the space is narrowed.

Fourth, the chemical is very unstable.

Generally, the life of a replenisher (life time) is generally two weeks, even with a floating lid. However, recently, the replenishment amount of each processing solution has been reduced, and in a minilab which processes an average of 30 color films a day, a replenishment solution of 10 L is often used for more than one month.

In such a case, the replenisher in the replenishment tank has a much higher rate of contact with air than the processing solution in the processing tank, resulting in deterioration. is happening. Therefore, 5L of refill tank
And the unit of the refill kit is reduced to 5L. In this case, there is a disadvantage that a packaging material is required.

Further, taking a color developing replenisher for color paper as an example, when preparing a color developing replenisher for color paper, a certain amount of water is put into a replenishing tank, and then a preservative-concentrating kit A is added. Is added and stirred, then the color developing agent-containing concentration kit B is added and stirred, then the alkali agent-containing concentration kit C is added and stirred, and finally, water is added to finish to a certain amount. At that time, some problems are likely to occur. For example, if the stirring is insufficient, or if you forget to add water first, crystals of the color developing agent tend to precipitate, and they are accumulated in the bellows pump and are not replenished, resulting in unstable photographic performance. Or the bellows pump is damaged. Concentration kits are not used immediately after production, but may be used one year after production. In some cases, color developing agents and preservatives are oxidized and their performance becomes unstable.

It is also known that color developing replenishers made from concentrate kits and powders also have some problems in replenishment tanks. For example, if the replenisher is not used for a long time, crystals will adhere to the refill tank wall,
In addition, the replenisher is easily oxidized and tar is generated. In addition, depending on the storage conditions, there is a problem that components that easily crystallize in the replenisher, for example, color developing agents, etc., precipitate at low temperatures. For this reason, some manufacturers specify the replenisher storage conditions and manage them by the user. The fact is that they are teaching.

As described above, the method of preparing a replenisher using a commonly used concentrating kit or the method of preparing a replenisher using a powder can be exemplified by a color developing solution for color paper. There are the above-mentioned problems, and there are similar problems with the bleach-fix solution, the bleach solution, and the fix solution. For example, the bleach-fix solution has a feature that storage stability is extremely poor. This is because the bleach-fixing process is a process immediately after a color developing solution having a high pH, and usually has a high acidity and a significantly low pH for the purpose of neutralization since this alkaline color fixing solution is carried by the paper to be processed. It is customary. At a low pH, it is said that a bleach-fix solution comprising a thiosulfate and an oxidizing agent has a remarkably poor preservability, and a low replenishment cannot be achieved by preparing a replenisher. The same applies to the fixing solution and the stabilizing solution.

As another problem, as the replenishment rate is reduced and the processing speed is increased, the replenisher solution is only concentrated, and the recent replenisher solution is usually concentrated to the limit of solubility.

[0025] This causes not only the storage stability of the replenisher to deteriorate, but also many practical problems such as crystal precipitation.

On the other hand, in addition to the above-mentioned method of preparing a replenisher using a concentrating kit or a powder, a method of directly replenishing a concentrating kit is known.

In this method, in order to improve the inefficiency of the dissolving operation, the concentration kit is directly replenished to the treatment tank using a supply means such as a bellows pump, and a certain amount of water is independently replenished. is there. Certainly, this method does not require a liquid preparation operation as compared with the above-mentioned method of preparing a replenisher from a concentration kit or a powder. Alternatively, since no replenisher is prepared, the problem of storage stability 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 causes a problem that the size of the automatic processing machine is increased. For example, taking the color paper processing solution CPK-2-20 as an example, there are three parts for the color developing replenisher kit, three parts for the bleach-fix replenisher, and three parts for the stable replenisher. The kit consists of two parts, which are supplied with 8 tanks for the concentration kit and 8 pumps
You need a unit. In the case of the conventional replenishment method, it is sufficient if there is a tank and a pump for each replenisher, so that three each are sufficient. Even in the case of supplying the enrichment kit in this way, more tanks and pumps are required compared to the conventional method,
Further, a pump for conditioning water is required. In addition, 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 components are rounded.

Furthermore, in the concentration kit, crystals are easily deposited near the outlet of the replenishing nozzle because of the concentrated solution, and maintenance is difficult. Further, the bellows pump does not have such a high supply accuracy, and in the case of replenishing the concentrated liquid, the replenishment accuracy is liable to be greatly deviated, resulting in a large fluctuation in photographic performance. Another problem is that the method of supplying the waste plastic container with the enrichment kit does not change the conventional replenishment method and the amount of waste plastic container.

Some proposals have been made to eliminate the plastic container and improve the chemical stability of the replenisher by a method other than the above.

For example, JP-A-58-11032 discloses a technique of encapsulating a developing component in microcapsules.
JP-61837 discloses a photographic tablet containing a disintegrant. Furthermore, JP-A-2-09042, JP-A2-109043,
JP-A-3-39735 and JP-A-3-39739 disclose a method using a granulated photographic processing agent having a certain average particle size.

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

JP-A-2-09042 discloses a granulated photographic processing agent having a certain average particle size.

However, the above-mentioned publication proposes an automatic developing machine which eliminates the work of dissolving the replenisher, simplifies the workability sufficiently and obtains stable photographic performance, and proposes a compact automatic processor without the replenishment tank. is not.

On the other hand, as a method of making the dissolving operation unnecessary in advance, Japanese Patent Laid-Open Publication No. 3-11344 discloses a method of extruding a paste-like part agent from each unit container in an amount corresponding to the mixing ratio of the part agent. A technique for accurately adjusting and supplying the diluted part agent to a predetermined concentration and supplying the same is disclosed. However, according to this method, the dissolving operation is reduced or almost completely eliminated, but the paste-like method is used. Since the part agent contains a solvent, it lacks stability, it is difficult to extrude a fixed amount over a long period of time, and if it is not used frequently, the nozzle is easily clogged, and it is difficult to keep the photographic performance constant. In addition, a container for containing the paste is required. In this case, a material that is flexible and hard to break 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 paste-like chemicals are often made into a paste with an organic solvent and have poor storage stability.

Japanese Utility Model Laid-Open No. 1-85732 discloses an automatic developing machine having a means for charging a tablet-type antibacterial agent into a stabilizing solution. Since there is no particular problem, it is not necessary to control the charging, and this is also not reminiscent of the processing agent replenishment control means.
This is not required since 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 other components are added as a liquid activator. Is related to regeneration, especially low replenishment as close to no overflow as possible, after removing and removing bromide ions and chloride ions from the developer with an ion exchange resin, the alkali agent activator and solid or small amount of insufficient components This is a method for adding a component without adding a concentrated color developing agent to increase the volume.

According to the present invention, the replenishment of the processing agent is performed only by the operation of putting the preliminarily divided and weighed solid processing agent into the processing tank, and is dissolved in the processing tank. The purpose of the present invention is completely different from that of the above-mentioned invention, and the present invention cannot be inferred.

On the other hand, it was also found that the solid processing agent had the following problems. Since the solid processing agent itself is composed of a material that is entirely dissolved in the processing liquid, it is easily susceptible to deterioration due to moisture, often moisture.

When this altered solid processing agent is introduced into the processing solution, it not only causes a reduction in the processing performance of the processing solution, but also causes various changes in the main body of the automatic developing machine, especially the solid processing agent supply means or storage means. Was found to be a problem. This is because the solid processing agent is partially dissolved by moisture, so that the solid processing agent supply device of the automatic developing machine
Alternatively, the components of the dissolved solid processing agent adhere to the storage means and become contaminated. Alternatively, for example, when the solid processing agent is a tablet or a pill, adjacent solid processing agents are bonded to each other by moisture, while, for example, when the solid processing agent is powder or granules, the solid processing agents are bonded to each other by moisture. Large masses were formed and so-called caking occurred, and in any case, if it was clogged in the charging section of the solid processing agent supply device into the processing tank, accurate charging could not be performed. And it turned out to be a problem. Also,
Regarding the processing performance, it has been found that an increase in the water content in the solid processing agent due to moisture promotes oxidation, sulfidation, and the like of the components in the solid processing agent, causing performance degradation and causing a problem.

Techniques for solving the above problems have been filed by the present applicant in Japanese Patent Application Nos. 3-267830 and 3-267831.
And Japanese Patent Application Nos. 3-267832 and 3-267833.

However, the above-mentioned application relates to an apparatus for preventing a solid processing agent in a supply device from getting wet due to rebound of the processing solution when the solid processing agent is directly introduced into a processing solution of an automatic developing machine. Yes, no consideration is given to the wetting of the solid processing agent due to the intrusion of steam generated from the automatic developing machine into the supply device and the alteration due to the wetness, or it is insufficient even if it is performed. Has become.

On the other hand, JP-A-4-213454 discloses that
In an automatic developing machine for adding a granular processing agent to a processing tank, an apparatus in which an outlet and a transport section are provided in a sealed dehumidifying space is disclosed. Until it is installed in the device, it can be protected from humidity by a method such as using a moisture-proofed package. However, once it is installed in the supply device, it takes one month for the automatic replenisher with low replenishment processing. During the above, it is possible that the state is maintained as it is. Here, for example, when the humidity of the outside air is high as in the summer of Japan, or when the automatic developing machine is installed in a region where humidity is generally high, such as a tropical region, the solid processing agent has a high humidity. No countermeasures against wetness and deterioration due to exposure to the outside air have been taken into account in the above-mentioned application.

In particular, when processing a photosensitive material by an automatic developing machine, the processing solution is adjusted to a constant temperature, so that the processing solution evaporates. Since the evaporation occurs, the condition near the automatic developing machine is likely to be in a high humidity condition as it is, and the above-mentioned problem is remarkably generated.

On the other hand, the following is a conventional problem.

In a conventional automatic developing machine in which a replenisher in which a processing agent is dissolved is prepared in advance, and the replenisher is supplied to the processing tank in a timely manner, the replenisher is dissolved or diluted in the replenisher operation. Water and water for correcting the evaporation of the processing liquid are required.

In order to take this water from a water supply source such as a tap into the automatic developing machine, a method of directly connecting the tap with the automatic developing machine is conceivable, but this requires strict installation conditions of the automatic developing machine and the water pipe. It is not generally used because it causes many problems such as being restricted. For this reason, in many cases, a method of transporting water manually from a nearby water supply source to an automatic developing machine has been adopted. However, this operation requires a great deal of effort for the user of the automatic developing machine, and especially when the water supply source is not close to the automatic developing machine, carries heavy water from a distance, and in some cases, downstairs. It is necessary and significantly reduces workability.

In recent years, the trend of automatic developing machines has been downsizing, and accordingly, automatic developing machines have been increasingly installed in places where conventional automatic developing machines were not installed. In general, in such places, many places do not have a water supply source nearby, and the water supply operation requiring labor as described above has been troublesome and troublesome.

In an automatic developing machine for directly dissolving the solid processing agent of the present invention in a processing tank, the processing amount of the photographic light-sensitive material is detected in the same manner as in the charging of the solid processing agent, replenishing water is supplied, and elution is caused by the processing. It is desirable to make the photographic performance constant by diluting the reaction-suppressing component thus obtained, and a water supply operation for this purpose is still required, which is a problem.

On the other hand, a method of dehumidifying air taken into an automatic processor and supplying the resulting water to a processing tank or a replenisher tank is described in JP-A-3-219245. Japanese Patent Application Laid-Open No. 4-78851 discloses an apparatus for supplying water obtained by condensing steam exhausted from the replenishing section and the processor section to the processor section. It is for obtaining water for correcting the evaporation of the water and the processing liquid for being a method and an apparatus for performing the processing while supplying the processing liquid into the processing tank,
The idea of securing the replenishing water in an automatic processor that dissolves the solid processing agent of the present invention directly in the processing tank and maintaining the system free of the need to prepare the replenishing solution cannot be recalled at all.

In a conventional method and apparatus for obtaining water by providing a dehumidifier or the like in an automatic developing machine which performs processing while supplying a replenisher from a replenisher tank in a conventional manner in a processing tank in a timely manner, In addition to the supply means for replenishment processing solution, supply control means, and tank, separately required for replenishment water, the same apparatus is used for an automatic developing machine that directly dissolves the solid processing agent of the present invention in a processing tank. The problem is that the entire automatic developing machine becomes complicated and large in size as compared with the case where it is provided.

Japanese Unexamined Patent Publication (Kokai) No. 3-219245 discloses a method for obtaining water by dehumidifying a gas taken in by a dryer. This method also supplies a replenisher to a treatment tank at an appropriate time. For obtaining water for dissolving or diluting the processing agent during preparation of the replenisher and water for correcting the evaporation of the processing solution, and the drying efficiency of the photosensitive material in the dryer. The idea is to ensure replenishment water in an automatic processor that dissolves the solid processing agent of the present invention directly in a processing tank, to make maintenance-free by eliminating the need for preparation of a replenisher, and to prevent deterioration of the solid processing agent due to humidity. Cannot be recalled at all.

On the other hand, Japanese Patent Laying-Open No. 4-78851 discloses another apparatus for returning water obtained by a steam condenser disposed above a treatment tank to a lower treatment tank. Is a method and apparatus for performing processing while supplying a replenisher from a replenisher tank to a processing tank in a timely manner, only for obtaining water for correcting the evaporation of the processing liquid, and the solid processing agent of the present invention. The idea of securing replenishing water in an automatic developing machine that dissolves water directly in a processing tank cannot be recalled at all.

Further, according to this technique, a condenser must be provided in each processing tank, which not only makes the entire automatic developing machine complicated and large, but also can compensate for a certain amount of evaporation. In order to supplement other water such as dilution water necessary for processing of the photosensitive material, complicated water supply work is still required.

[0055]

SUMMARY OF THE INVENTION The object of the present invention is as follows.
Another object of the present invention is to achieve practical use of an automatic developing machine capable of using a solid chemical without complicated operation for a user by eliminating a liquid chemical which causes a danger in transportation and handling.

Secondly, there is an automatic developing machine in which a completely automatic replenishment system is completed by eliminating the manual dissolving operation of the concentration kit by the user himself.

Third, there is a need for a compact automatic developing machine which eliminates many built-in replenishment tanks.

Fourth, an object of the present invention is to achieve an automatic developing system with improved processing stability which eliminates the necessity of storing a liquid replenisher.

Fifth, it is an object of the present invention to achieve a low-pollution system in which the use of a plastic packaging material is eliminated by eliminating the use of a plastic bottle for liquid.

Sixth, an object of the present invention is to achieve an automatic developing machine capable of always maintaining high-quality solid processing agents to be charged.

Seventh, the object is to achieve an automatic developing machine capable of saving labor for supplying water necessary for processing.

[0062]

The present inventors have conducted various studies to solve the above problems, and as a result, have found that the following structure can solve and achieve the above problems.

[0063] That is, the object is achieved, (1) a processing bath for accommodating a processing solution for processing an exposed silver halide photographic light-sensitive material, a housing means to accommodate the pre-divided weighed solid processing agent, wherein Supply means for directly charging the divided and weighed solid processing agent into a processing tank; processing amount detection means for detecting processing information of the silver halide photographic light-sensitive material; and the silver halide detected by the detection means Control means for controlling and operating the supply means in accordance with the processing amount information of the photographic light-sensitive material and introducing a solid processing agent ;
A gas-in-gas separation device for separating water and discharging dry air , wherein the water separated by the gas-in-gas separation device is provided.
Having a replenishing device for supplying and recycling the processing tank,
First, the dry air generated simultaneously by the moisture separation device in gas.
Introducing air into the supply means and / or the storage means
This is achieved by an automatic developing machine for a silver halide photographic light-sensitive material , characterized by having means .

In a preferred embodiment of the present invention, (2) the solid processing agent is a powdery, granular, or tableted tablet which has been divided and weighed in advance. (3) The automatic developing device for a silver halide photographic light-sensitive material according to (1) or (2), wherein the water-in-gas dividing device takes in a gas outside the automatic developing device. (4) An automatic developing machine for a silver halide photographic light-sensitive material, wherein (4) the apparatus for dividing moisture in a gas sucks gas in a drying section of the automatic developing machine.
(3) The automatic developing machine for a silver halide photographic light-sensitive material according to any one of (3), (5) wherein the water-in-gas dividing device sucks a gas in an upper part of a processing tank of the automatic developing machine. The automatic developing machine for a silver halide photographic light-sensitive material according to any one of (1) to (4), wherein (6) the apparatus for separating moisture in a gas is as follows:
(C) at least one device or system selected from
Any of (1) to (5), characterized in that
Automatic development for a silver halide photographic light-sensitive material according to claim 1.
Machine .

(A) Apparatus or system for condensing gas by heat pump (b) Apparatus or system for condensing gas by electronic cooling element (c) Separation of water by semi-permeable membrane for separating water vapor from gas Equipment or method.

[0066]

The present inventors have conducted enormous experiments concerning the direct injection of the solid processing agent into the tank, and determined the optimum replenishing amount of the processing agent to be added at one time so as not to change the photographic performance of each processing solution. Was. This optimum replenishment amount was thought to depend on the size of the processing tank of the automatic developing machine, that is, the volume of the processing solution. The concentration does not rise
It has been discovered that replenishment water can be injected in time with dissolution and has the advantage of creating extremely stable photographic performance. It turned out that it was common sense to melt and use it.

The amount of the processing agent added at one time is preferably 0.1 to 50 g, 1 to 20 g for a color developing solution, 5 to 50 g for a fixing solution or a bleach-fixing solution, and 0.1 to 10 g for a stabilizing solution.
However, in the case of a black-and-white developer, the amount is particularly preferably 0.5 to 20 g, and a solid processing agent in this range is directly introduced into a processing tank of a general small-sized developing machine, and does not adversely affect the photographic state even when the processing is performed while slowly dissolving. . Because, as mentioned above, the solid processing agent does not dissolve rapidly but dissolves slowly, so even if the amount added at a time is large, the composition is balanced to the amount consumed during processing and a stable processing performance is achieved. It is because it shows. It was found that the photographic performance could be kept constant by injecting the replenishing water along with the dissolution. This is
It was an amazing discovery that no one noticed. In the present invention, the solid processing agent is directly charged into the processing tank, but the processing liquid is always adjusted to the processing temperature, and is 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 are achieved. It has been found that this has the great advantage that the insolubility phenomenon seen when dissolving in cold water does not appear. The insoluble phenomenon named by the present inventors is a solidification phenomenon that occurs when a solid processing agent is poured into cold water at a time and is stirred slowly or almost without stirring, and indicates that it appears in a vitrified state. As a result, it was found that the solution was not dissolved for a long time even with strong stirring. On the other hand, in hot water dissolution at the processing temperature of an automatic developing machine, a phenomenon was discovered in which even if a solid processing agent was added more and more, the solid processing agent was sequentially dissolved and the present invention was completed.

In the present invention, it is desirable to provide a replenishing water supply means. However, it is desirable that the replenishing water supply means be controlled in the same manner by the processing amount detection stage of the photographic light-sensitive material necessary for controlling the supply of the solid processing agent. However, it should be emphasized that the replenishing water is not water for dissolving the solid processing agent. That is, the solid processing agent is intended to compensate for the consuming component originally lacked by the processing, and the replenishing water is intended to dilute the reaction-inhibiting component eluted by the processing and to maintain a constant photographic performance. Is exactly the opposite. In the past, water was used to dissolve chemicals by chance, but as stated above, the original purpose is to compensate for the accumulated components eluted by the reaction while supplementing the water taken out by the photographic material and the water evaporated from the tank surface. It is for thinning. Therefore, it can be controlled separately from the introduction of the solid processing agent. However, if controlled by the processing amount detection means, the sensor can be omitted, which is preferable.

Therefore, in the present invention in which the solid processing agent is directly charged into the processing tank, only the water necessary for adjusting the replenisher in the prior art is unnecessary, and as a result, the side effect that overflow is reduced is large. I understand.
Conventionally, there has been a common sense that the replenisher must be adjusted in advance, so that the replenisher has been concentrated as much as possible to compensate for the component. Even though it is known that the replenishing amount can be reduced as the concentration becomes higher and the overflow waste liquid, which is an environmental problem, can be reduced, the solubility of the treatment chemical becomes a large barrier, and this cannot be achieved. According to the present invention, the chemicals have substantially only the tank liquid concentration, there is no higher concentration state than the tank liquid, and only the necessary processing chemicals are replenished. Therefore, replenishment can be performed without overflow at all.

However, as described above, it is preferable to use replenishing water in order to reduce the accumulation of the reaction-inhibiting components, in particular, the concentration of halide ions in the developing solution and silver ions in the fixing solution and the bleach-fixing solution. The replenishment water is used for the purpose of diluting these reaction-inhibiting components, and can independently compensate for the water content of each processing solution brought out by the photographic material or lost by evaporation from the tank surface, which is the processing stability of the present invention. Contribute significantly.

Accordingly, the control information used to supply the replenishing water includes the processing amount (for example, area) of the photographic material to be processed, the operation time, the temperature adjustment time, the stop time, the environmental temperature and the humidity (relative humidity) of the installation place. If the amount of replenishment water added is controlled based on such information, the chemical components in the processing tank can be controlled in an ideal state, and the photographic performance is not good. It can be said that this is a periodical management method. The reason for this is that conventionally, as the replenishment at a lower level is advanced, the processing agent component is concentrated due to the effect of evaporation from each tank, which has been a serious problem. Generally, the most preferable method for correcting evaporation is to dilute the replenisher and replenish the replenisher in a large amount. However, this method has a drawback that it increases the amount of overflow waste liquid and is not environmentally preferable. Was. If the replenisher is used for the evaporation correction, it is the same as the replenisher enters even though it is not processed, and the concentration of the components also increases. So the morning liquid level dropped,
The way of replenishing water and leveling liquid was common,
This is not to replenish the evaporation with water but only to add water to the processing liquid in the tank whose volume has been reduced due to a change in temperature, and has not reached a fundamental solution at all.

The correct evaporation correction is to ensure that the components remain the same except for the consumption by the photographic material, evaporating the water vapor generated by the tank liquid temperature and the vapor pressure on the tank surface with or without processing. It is to supply according to the quantity.

That is, in the present invention, the supply of the replenishing water is performed for the following three purposes. The purpose is to dilute the accumulated harmful substances eluted by the reaction when the photosensitive material is processed, and to dilute the moisture taken out by the processed photographic material or unnecessary chemicals brought in from the pre-solution for the purpose of keeping the concentration constant. The water is supplied for the purpose of thinning, and for the purpose of replenishing the water evaporated from the tank surface. It is controlled and executed. This method is a new method that has never existed before and is made possible by the present invention. It has been found that this water replenishment means of the present invention dramatically improves processing stability. In the present invention, the solid processing agent is divided and weighed in advance into a predetermined amount, preferably a predetermined amount. For this reason, the processing by the automatic developing machine of the present invention has high replenishment accuracy and exhibits extremely stable continuous processing performance. The term "previously divided and weighed" means that the treatment agent has been divided and weighed to a predetermined amount before the processing agent is stored in the automatic processing machine of the present application or before the packaging material containing the processing agent is set on the fixing means. For example, it refers to a mode in which tablets or pills of a predetermined size are formed, or a mode in which granules or powder are subdivided and packaged by a predetermined amount. It does not include a mode in which powders and granules are put in a storage means, and a single charge is measured at the time of supply. In the conventional replenisher supply and replenishment system, replenishment is performed by a bellows pump, but the accuracy of this pump is not constant and is not originally suitable for precise replenishment control. On the other hand, the solid processing agent in the case of the present invention is weighed and divided into a certain amount in a processing agent production plant, for example, and is produced. The replenishment control is ON / OFF control of whether or not the solid processing agent is supplied. There is no variation. Therefore, the precision of the supply of the processing agent is remarkably high, so that a stable processing performance can be obtained. Solid processing agent of the present invention, powder, granules, tablets,
Pills and the like may be used, and there is no problem in mixing these. The object of the present invention can be attained by using a liquid, which is safe, such as water which does not become a dangerous substance. Tablets and pills are particularly preferable for divided weighing, and in the case of granules and powders, it is preferable that they are individually weighed and then individually packaged with an alkali-soluble film, plastic film, paper, or the like.

In other words, tablets and pills can be supplied by themselves with high precision divided and weighed, and in the form of powder or granules, the solid processing agent of the present invention is completed by separately weighing and packaging individually.

Here, in the present invention, since the automatic developing machine has the moisture separating device in gas, the dehumidification and drying of the air in the vicinity of the automatic developing machine, especially the solid processing agent supply device of the automatic developing machine, is performed. By doing so, wetting of the solid processing agent stored in the solid processing agent supply device due to humidity, deterioration of the quality can be significantly suppressed. For example, in the case of tablets and pills, tablets and pills that are closer to each other due to moisture can be removed. It is possible to prevent a situation in which a predetermined amount or more is thrown in at the time of throwing in even though the weighing is divided into a predetermined amount in advance, and the feeding section is clogged and is not thrown at all.

Further, by introducing the obtained dry gas into the solid processing agent supply device, wetting and alteration of the solid processing agent stored in the solid processing agent supply device due to humidity can be significantly suppressed. Can be.

When the solid processing agent is a powder or a granule, in the present invention, individual packaging is particularly required only for the purpose of dividing into a certain amount, and therefore, paper having little moisture-proof property is used as the packaging material. Although it is possible to achieve the object of the present invention by this, tablets and pills can be coated with a water-soluble moisture-proof polymer, or can be further moisture-proof by using a moisture-proof material, powder and For granules, by selecting a moisture-proof material for each packaging material,
It has been found that the object of the present invention is more preferably achieved.

As the apparatus for separating moisture in gas in the present invention, a commercially available dehumidifier can be used, and furthermore, a device or a system for condensing gas by a heat pump or an electronic cooling element and a Peltier element can be used. It is also possible to use a device that is configured. Also,
It is also possible to use a device or a system that separates water by a semi-permeable membrane that separates water vapor from a gas. The device is described in Chemical Engineering, Vol. 53, No. 1 (1989) 51.
Pp. 53.

It is also possible to use the above-mentioned devices and methods in combination.

The most efficient timing of the operation of the water-in-gas separation apparatus is when the vicinity of the automatic developing machine or when the upper part of the processing tank and the drying section are at high humidity, that is, when the automatic developing machine is operating. Since water can be obtained, it is preferable to operate the apparatus in conjunction with the operation of the processing apparatus, and it is possible to perform such control. Further, even when the automatic developing machine is not operating, when the humidity near the automatic developing machine is high as in the summer of Japan, it is preferable to operate the water-in-gas separation device. In particular, as this control system, the humidity in the solid processing agent supply device is detected, and the moisture in gas separation device is controlled so as to maintain a constant low humidity,
It is preferable to operate.

In the automatic developing machine of the present invention, it is a preferred embodiment to provide a replenishing water supply means, a replenishing water supply control means, and a replenishing water tank, respectively. By using these means, it is possible to use the apparatus without providing a special device, and it is possible to save water supply work without impairing the compactness of the automatic developing machine.

This is a method of obtaining moisture by providing a moisture separating device such as a dehumidifier in an automatic developing machine for processing a photosensitive material while supplying a replenishing solution from a conventional replenishing solution tank to a processing tank in a timely manner. In addition, in the apparatus, in addition to the supply means for the replenishment processing solution, the supply control means, and the tank, separate means for the replenishment water are required, and the water supply work can be certainly reduced. The problem that the machine becomes large and complicated was solved at once by using a solid processing agent, and the present invention was achieved.

Further, the gas-in-gas separation device is configured to suck in the gas in the drying section of the automatic developing machine so that high-humidity air is taken into the gas-in-gas separation device during operation of the automatic developing machine. Not only can water be obtained efficiently, but also prevent the discharge of high-humidity air to the outside of the automatic developing machine, and by keeping the vicinity of the solid processing agent at low humidity, storage stability is improved. Thus, the object of the present invention can be achieved more effectively.

The same effect as in the case where the gas in the drying section is sucked is obtained by configuring the water-in-gas separation apparatus to suck the gas in the upper part of the processing tank of the automatic developing machine. The object of the present invention can be achieved more efficiently.

Further, the same effect as in the above two cases is exhibited by configuring the water-in-gas separation apparatus so that the gas can be circulated into the solid processing agent supply apparatus.
The object of the present invention can be achieved more efficiently.

The solid processing agent according to the present invention is a powder processing agent as described above or a solid processing agent such as tablets, pills and granules, etc., which has been subjected to a moisture-proof treatment as required. Pastes and slurries are semi-liquid and inferior in storage stability, and do not include those having a shape that is regulated with the danger of transportation, and are not included in the solid processing agent of the present invention.

The term “powder” used in the present invention refers to an aggregate of fine crystal grains. The granules in the present invention are obtained by adding a granulating step to a powder, and refer to granules having a particle size of 50 to 5000 μm. The tablet referred to in the present invention refers to a tablet obtained by compressing powder or granules into a certain shape.

Hereinafter, the present invention will be described in more detail.

Among the above solid processing agents, tablets are preferred
It is preferably used because of high replenishment accuracy and easy handling.

To solidify the photographic processing agent, a concentrated liquid or a fine or granular photographic processing agent and a water-soluble binder are kneaded and molded, or the water-soluble binder is added to the surface of the temporarily formed photographic processing agent. Any means can be adopted such as forming a coating layer by spraying or the like (Japanese Patent Application Nos. 2-135887, 2-203165,
2-223166, 2-203167, 2-203168, 2-304
09).

A preferred tablet production method is a method in which a powdery solid processing agent is granulated and then subjected to a tableting step to form the tablet. There is an advantage that the solubility and storage stability are improved and the photographic performance becomes stable as compared with a solid processing agent formed by simply mixing a solid processing agent component and forming a tablet.

The granulation method for tablet formation is to use a known method such as tumbling granulation, extrusion granulation, compression granulation, crushing granulation, stirring granulation, fluidized bed granulation, and spray drying granulation. Can be done.
For tablet formation, the average particle size of the obtained granules is 100 to 800 μm in that, when the granules are mixed and pressed and compressed, non-uniformity of components, so-called segregation is unlikely to occur. It is preferable to use one, more preferably 200 to 750 μm
It is. Furthermore, the particle size distribution is ± 10% for more than 60% of the granulated particles.
Those having a deviation of 0 to 150 μm are preferred. Next, when the obtained granules are compressed under pressure, a known compressor such as a hydraulic press, a single-shot tableting machine, a rotary tableting machine, and a pre-ketting machine can be used. The solid processing agent obtained by pressurizing and compression can take any shape, but from the viewpoint of productivity, handleability, or the problem of dust when used on the user side, a cylindrical, 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 such as 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,
51-61837, 54-155038, 52-88025, UK Patent 1
213808 can be produced by a general method described in the specification, and further, granule treating agents are, for example, JP-A-2-109042,
It can be produced by a general method described in the specifications such as Nos. 109043, 3-39735 and 3-9739. Furthermore, powder processing agents, for example, JP-A-54-133332, British Patent 725892,
It can be produced by a general method as described in the specifications such as US Pat. No. 7,229,862 and German Patent 3,733,861.

[0095] The bulk density of the above solid processing agent is determined in the case of a tablet from the viewpoint of its solubility and the effect of the object of the present invention.
1.0g / cm ³ ~2.5g / cm ³ is in terms of the strength of 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 from 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 developers, black-and-white developers, bleaching agents, fixing agents, bleach-fixing agents, stabilizers, and the like. The color developing agent has a large stabilizing effect.

In addition, black and white developers, color developers, 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 solidified, but it is preferable that at least the color developer is solidified. That is, the effects of the present invention are most remarkably exhibited because the color developing component contains a large number of components that cause a mutual chemical reaction and also contains harmful components. More preferably, in addition to the color developing agent, the bleach-fixing agent, or the bleaching agent and the fixing agent are solid processing agents. These have conventionally been regarded as having a problem in transportation in a liquid packaging kit.

The solid processing agent used in the present invention may be such that only one part of a certain processing agent is solidified, but it is preferable that all the components of the processing agent be solidified. is there. It is desirable that each component is molded as a separate solid processing agent and is mounted in the same unit. It is also desirable that the separate components are packaged in the order in which they are periodically and repeatedly placed in a package.

It is preferable that all the processing agents to be replenished into each processing tank according to the processing amount information are charged as solid processing agents.
When replenishing water is required, replenishing water is replenished based on the processing amount information or other replenishing water control information. In this case, the liquid to be replenished to the treatment tank can be only replenishing water. That is, when two or more types of processing tanks need replenishment, only one tank is required to store the replenishing liquid by sharing the replenishing water, and the size of the automatic developing machine can be reduced. In particular, it is preferable to place one replenishing water tank outside outside in order to make the automatic processing machine compact.

In the case of solidifying the color developing agent, it is preferable that the alkali agent, the color forming agent and the reducing agent are all converted into a solid processing agent, and in the case of tablets, at least three agents are used and most preferably one agent. It is a preferred embodiment of the solid processing agent used. When the solid processing agent is divided into two or more agents, it is preferable that these tablets and granules are packaged in the same manner.

When the tablets and pills are moisture-proof-packaged, the following materials can be used.

As synthetic resin materials, polyethylene (either high-pressure method or low-pressure method), polypropylene (either unstretched or stretched), polyvinyl chloride, polyvinyl acetate, nylon (stretched, unstretched), polychlorinated Vinylidene, polystyrene, polycarbonate, vinylon, eval, polyethylene terephthalate (PET), other polyesters, rubber hydrochloride, acrylonitrile butadiene copolymer, epoxy-phosphate resin (JP-A-63-63037)
Or the polymer described in JP-A-57-32952). Or pulp may be used.

These are usually laminated and adhered to the film, but may be used as a coating layer.

Further, it is more preferable to use various gas barrier films, for example, using an aluminum foil or an aluminum vapor-deposited synthetic resin between the above synthetic resin films.
The total oxygen permeability of these laminated films is 50 ml / m ² 24h
r / atm or less (at 20 ° C and 65% RH), more preferably 30ml / m ² 24
It is preferably at most hr / atm.

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

The above synthetic resin film may be a one-layer (polymer) resin film or two or more laminated (polymer) films.
It may be a resin film.

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

Next, examples of the laminated polymer resin film satisfying the conditions of the present invention include (4) PET / polyvinyl alcohol / ethylene copolymer (EVAL) / polyethylene (PE), and (5) drawn polypropylene ( (6) Unstretched polypropylene (CPP) / Eval / PE, (7) Nylon (N) / Aluminum foil (Al) /
PE, (8) PET / Al / PE, (9) Cellophane / PE
/ Al / PE, (10) Al / paper / PE, (11) PET / PE
/ Al / PE, (12) N / PE / Al / PE, (13) paper / P
E / Al / PE, (14) PET / Al / PET / polypropylene (PP), (15) PET / Al / PET / high density polyethylene (HDPE), (16) PET / Al / PE / low density polyethylene (LDPE ), (17) Evar / PP,
(18) PET / Al / PP, (19) paper / Al / PE, (20) P
E / PVDC coated nylon / PE / Ethyl vinyl acetate / polyethylene condensate (EVA), (21) PE / P
VDC coated N / PE, (22) EVA / PE / aluminized nylon / PE / EVA, (23) aluminum-deposited nylon / N
/ PE / EVA, (24) OPP / PVDC coated N / P
E, (25) PE / PVDC coated N / PE, (26) OPP /
EVAL / LDPE, (27) OPP / EVAL / CPP,
(28) PET / Eval / LDPE, (29) ON (stretched nylon) / Eval / LDPE, (30) CN (unstretched nylon) / Eval / LDPE, etc.
(30) is preferably used.

As a more specific configuration of the packaging material, if the side in contact with the treatment agent is the inner surface, the PE / PE
Main paperboard / PE / Al / epoxy-phosphate resin layer / polyester resin layer / PE, PE / K-nylon / PE or adhesive / Al / PE / paperboard / PE, PE /
Vinylon / PE or adhesive / Al / PE / paperboard / P
E, 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.

As a method for moisture-proof packing of tablets and granules, there is a 4-side seal 3-way seal stick (pillow package, gusset package) PTP cartridge.

The four-sided seal, the three-sided seal, and the stick (pillow, gusset) packaging are different in form, and the above-mentioned materials are used. However, when used in the peel-open system, a sealant agent is laminated to have the peel-open suitability. .

The peel-open method generally includes a cohesive failure method, an interfacial peeling method, and an interlayer peeling method.

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

The surface-active peeling method is a method of peeling at an interface between films, in which the sealing film (sealant) and the adherend are not completely fused and can be peeled with an appropriate strength. The sealant is a film in which an adhesive resin is mixed, and polyethylene, polypropylene or a copolymer thereof, polyester, or the like can be selected depending on the material of the adherend.

The delamination method is to peel the sealant between the layers of the laminated film using a multilayer co-extruded film such as a laminated film.

In the peel-open system using the film of the present invention, an interlayer peeling system or an interface peeling system is preferable.

Also, since such a sealant is thin,
Normally, other films such as polyethylene, polypropylene, polystyrene, polycarbonate, polyester (polyethylene terephthalate), polyvinyl chloride, nylon, eval, and aluminum are laminated and used. Consider moisture proofness, environmental compatibility, and matching with the contents. Polyethylene, polypropylene, polyester, eval and the like are preferred. In consideration of printability, the outermost surface is preferably made of unstretched polypropylene polyester or paper.

Examples of the sealant film include Tocello, CMPS film, Dai Nippon Ink's Diflan PP-100, PS-300 or letterpress LTS film.
There are Sun Seal FR and Sun Seal MS manufactured by San-A Chemical Co., and the types already laminated with polyester include Diclan C-1600T and C-1602T.

PTP is a packaging form in which a solid processing agent is placed in a sheet of PVC, CPP, or the like, which is formed as a type of blister packaging, and heat-sealed with an aluminum sealing material.

Environmentally, PVC is not used as a forming material. Recently, A-PET or highly moisture-proof PP (for example, TAS)
-1130, TAS-2230, TAS-3230: Taisei Kako Co., Ltd.)
Is preferably used.

When the treating agent is packaged, bound or covered with a water-soluble film or binder, the water-soluble film or binder may be a polyvinyl alcohol-based, methylcellulose-based, polyethylene oxide-based, starch-based, polyvinylpyrrolidone-based, Hydroxypropylcellulose, pullulan, dextran and gum arabic,
Polyvinyl acetate-based, hydroxyethylcellulose-based, carboxyethylcellulose-based, carboxymethylhydroxyethylcellulose sodium salt-based, poly (alkyl) oxazoline-based, polyethylene glycol-based film or binder is preferably used, among these, Particularly, polyvinyl alcohol-based and pullulan-based ones are more preferably used from the viewpoint of the effect of coating or binding.

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

The method for producing these water-soluble films is described, for example, in JP-A-2-124945, JP-A-61-97348 and JP-A-60-15824.
No. 5, JP-A-2-86638, JP-A-57-117867, JP-A-2-7
No. 5650, JP-A-59-226018, JP-A-63-218741, and JP-A-54-1
It is produced by a general method as described in the specification of No. 3565 and the like.

Further, as these water-soluble films, those commercially available under the names of Sorblon (manufactured by Aicello Chemical Co., Ltd.), Hicelon (manufactured by Nichigo Film Co., Ltd.) and Pullulan (manufactured by Hayashibara) can be used. Also, Chris Craft Industries In
c. The 7-000 series polyvinyl alcohol films available from MONO-SOL, Inc., dissolve at a water temperature of about 34 ° F. to about 200 ° F., are harmless, exhibit high chemical resistance, and are particularly preferred. Used.

The thickness of the water-soluble film is preferably from 10 to 120 μm in view of the storage stability of the solid processing agent, the dissolution time of the water-soluble film and the precipitation of crystals in an automatic developing machine. Are preferred, especially 20
の も の 60μ is preferably used.

Further, the water-soluble film is preferably thermoplastic. This is because not only the heat sealing process and the ultrasonic welding process are facilitated, but also the covering effect is more excellent.

The tensile strength of the water-soluble film is 0.5
× 10 ⁶ to 50 × 10 ⁶ kg / m ² is preferable, especially 1 × 10 ^{6 to} 25 × 10
Preferably ⁶ kg / m ^2, more especially ^{1.5 × 10 6 ~10 × 10 6} kg /
m ² is preferred. These tensile strengths are measured by the method described in JIS Z-1521.

The photographic processing agent packaged or bound or coated with a water-soluble film or binder can reduce atmospheric humidity such as high humidity, rain and fog, and water during storage, transportation and handling. It is preferable that the moisture-proof packaging material is wrapped with a moisture-proof packaging material in order to prevent damage from sudden contact with water due to wet or wet hands, and the moisture-proof packaging material is preferably a film having a thickness of 10 to 150 μm. The material is polyethylene terephthalate, polyethylene, polyolefin film such as polypropylene, kraft paper, wax paper, moisture-resistant cellophane, glassine, which can have moisture resistance effect with polyethylene,
Polyester, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyamide, polycarbonate, acrylonitrile and metal foils such as aluminum, preferably at least one selected from metallized polymer films, and a composite material using these There may be.

In the practice of the present invention, it is also preferable to use a degradable plastic, particularly a biodegradable or photodegradable plastic, as the moisture-proof packaging material.

Examples of the biodegradable plastics include those composed of natural polymers, polymers produced by microorganisms, synthetic polymers having good biodegradability, and blending of biodegradable natural polymers with plastics. ,
Examples include those in which a group that is excited by ultraviolet light and is linked to cleavage is present in the main chain. Further, in addition to the polymers listed above, those having both functions of photodegradability and biodegradability can be used favorably.

The following are specific examples of these specific examples.

Examples of biodegradable plastics include natural polymer polysaccharides, cellulose, polylactic acid, chitin, chitosan, polyamino acids, and modified products thereof. Microbial polymers such as PHB-PHV (3-hydroxybutyrate and 3-hydroxyvale). Biopol), which is composed of
Microbial-produced cellulose etc.Biodegradable synthetic polymers Polyvinyl alcohol, polycaprolactone, etc., or copolymers / mixtures of them Blend of biodegradable natural polymers into plastics There is cellulose, which has a shape-disintegrating property in addition to plastic.

Examples of photodegradability include the introduction of a carbonyl group for photodisintegration, and an ultraviolet absorber may be added to promote disintegration.

With respect to such degradable plastics,
"Science and Industry" Vol. 64, No. 10, pp. 478-484 (1990),
“Functional materials”, generally described in July 1990, pp. 23-34, can be used. In addition, Biopol (Biopol) (manufactured by ICI), Eco (Eco) (manufactured by Union Carbide), Ecolite (Ecolight) (manufactured by Eco Plastic), Ec
Commercially available decomposed plastics such as ostar (Ecostar) (St. Lawrence Starch) and Knuckle P (Nippon Unicar) can be used.

The moisture-proof packaging material preferably has a moisture permeability coefficient of 10 g · mm / m ² 24 hours or less, more preferably 5 g · mm / m ² 24 hours or less.

In the present invention, as the supply means for supplying the solid processing agent to the processing tank, for example, when the solid processing agent is a tablet, Japanese Unexamined Patent Publication Nos. 63-137783 and 63-97522,
There is a known method such as Japanese Utility Model Laid-Open No. 1-85732, but any method may be used as long as the function of supplying tablets to the processing tank is provided at a minimum. When the solid processing agent is in the form of granules or powder, Japanese Utility Model Application Laid-Open Nos. 62-81964 and 63-84151,
No. 292375, gravity drop method described and actual opening 63-105159,
The method using a screw or a screw described in JP-A-63-195345 or the like is a known method, but is not limited thereto.

However, in a preferred method, the supply means for supplying the solid processing agent to the processing tank is such that a predetermined amount of the solid processing agent weighed in advance and divided and packaged is opened and taken out of the package according to the processing amount of the photosensitive material. A method is conceivable. Specifically, the solid processing agent is sandwiched and stored in a predetermined amount, preferably in a single replenishment amount, in a package composed of at least two packaging materials, and the package is separated in two directions or the package is separated. A part is opened to make it ready for removal. The solid processing agent in a removable state can be easily supplied to a processing tank having a filtering means by natural fall.

As an embodiment, it is conceivable that a package made of at least two packaging materials is closely adhered or adhered to each other so as to sandwich the solid processing agent so as to be able to separate the periphery of the solid processing agent. . By pulling each packaging material sandwiching the solid processing agent in a different direction, the contact surfaces adhered or adhered are separated, and the solid processing agent can be taken out.

As another embodiment, a configuration is conceivable in which at least one of the packages made of at least two packaging materials can be opened by an external force so as to sandwich the solid processing agent. The term “opening” as used herein refers to a cut or break that leaves a part of the packaging material. As an opening method, the solid processing agent is forcibly extruded by applying a compressive force from the non-opening side package to the openable package through the solid processing agent, or the package is opened. It is conceivable that the solid processing agent can be taken out by making a cut with a sharp member.

The supply start signal is obtained by detecting information on the processing amount. Further, the driving means for separating or opening the package operates based on the obtained supply start signal. The supply stop signal is obtained by detecting information indicating that a predetermined amount of supply has been completed. Further, based on the obtained supply stop signal, control is performed such that the driving means for separating or opening is stopped.

The supply means of the solid processing agent has a control means for supplying a fixed amount of the solid processing agent in accordance with the processing amount information of the photosensitive material, which is an important requirement in the present invention.
That is, in the automatic developing machine of the present invention, it is necessary to keep the component concentration in each processing tank constant and to stabilize photographic performance. What is the processing amount information of silver halide photographic light-sensitive materials?
It is a value proportional to the processing amount of the silver halide photographic light-sensitive material processed with the processing solution, the processing amount of the processed silver halide photographic light-sensitive material, or the processing amount of the silver halide photographic light-sensitive material being processed. It indicates indirectly or directly the amount of reduction of the treating agent in the liquid. The detection may be performed at any time before or after the photosensitive material is carried into the processing solution, or during immersion in the processing solution. The amount of the photosensitive material printed by the printer may be used. Further, the concentration may be a concentration or a change in concentration of the processing liquid stored in the processing tank. Alternatively, the amount of the treatment liquid that has come out after drying may be used.

The place where the solid processing agent of the present invention is charged may be in a processing tank, but is preferably in communication with a processing section for processing a photosensitive material, and a processing liquid flows between the processing section and the processing section. And a structure in which there is a constant processing solution circulation amount with the processing unit and the dissolved components move to the processing unit. The solid processing agent is preferably introduced into a processing liquid whose temperature is controlled.

Generally, in order to control the temperature of the automatic developing machine, the processing liquid is controlled by an electric heater. A heat exchange section is provided in an auxiliary tank connected to a processing tank as a processing section. Is provided with a pump for feeding the liquid from the processing tank at a constant circulation amount and for keeping the temperature constant.

Usually, a filter is disposed for the purpose of removing crystal foreign substances that are mixed in the processing solution or generated by crystallization, and play a role of removing the foreign substances.

The most preferable method is to put a solid processing agent into a place where the temperature is controlled, such as a place communicating with the processing section, such as the auxiliary tank. The reason for this is that the insoluble components of the input processing agent are blocked from the processing unit by the filter unit, and the solid content can be prevented from flowing into the processing unit and adhering to the photosensitive material.

In the case where the processing agent charging section is provided together with the processing section in the processing tank, it is preferable to devise a shield or the like so that the insoluble portion does not directly contact the film or the like.

As the materials of the filter and the filtration device, those used in general automatic developing machines can be used in the present invention, and the special structure and material do not affect the effects of the present invention.

The present invention eliminates the need for a tank or the like for storing the replenisher by charging the solid processing agent into the processing tank, making the automatic processing machine compact and, when the circulation means is provided, dissolving the solid processing agent. The properties are also very good.

As the color developing agent used in the color developing agent of the present invention, a p-phenylenediamine compound having a water-soluble group is preferably used because it exhibits the desired effects of the present invention and has little fogging. Can be

The p-phenylenediamine-based compound having a water-soluble group has less contamination of the photosensitive material and has less skin contact than a para-phenylenediamine-based compound having no water-soluble group such as N, N-diethyl-p-phenylenediamine. In addition to having the advantage that the skin is less susceptible to fogging, the object of the present invention can be more efficiently achieved by combining it with the color developing solution of the present invention.

Examples of the water-soluble group include those having at least one amino group on the p-phenylenediamine compound or the benzene nucleus. Specific examples of the water-soluble group include — (CH ₂ ) _n —CH ₂ OH ,-(CH ₂ ) _m -NHSO _2- (CH ₂ ) _n CH ₃ ,-(CH ₂ ) _m -O- (CH ₂ ) _n -CH ₃ ,-(CH ₂ CH ₂ O) _n C _m H _{2m +1} (m and n each represent an integer of 0 or more), a —COOH group, a —SO ₃ H group and the like are preferable.

Specific examples of the color developing agent preferably used in the present invention include (C-1) to (C-16) described in Japanese Patent Application No. 2-203169, pages 26 to 31. Is mentioned.

The above color developing agents are usually used in the form of salts such as hydrochloride, sulfate and p-toluenesulfonate.

The color developing agents may be used alone or in combination of two or more, and if desired, a black and white developing agent such as phenidone, 4-hydroxymethyl-4-methyl-1-phenyl
It may be used in combination with -3-pyrazolidone or methol.

Further, in the present invention, when the compounds represented by the following general formulas [A] and [B] are contained in the color developer according to the present invention, the effects of the present invention are exhibited more favorably. .

That is, when a solid processing agent is used, it is effective in that not only the preservability of the solid processing agent such as a tablet but also the strength can be maintained as compared with other compounds, and the photographic performance is stable and unsatisfactory. There is also an advantage that fog generated in an exposed portion is small.

[0158]

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In the general formula [A], R ₁ and R ₂ are not hydrogen atoms at the same time but are each an alkyl group, an aryl group,

[0160]

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Or a hydrogen atom, the alkyl groups represented by R ₁ and R ₂ may be the same or different, and each is preferably an alkyl group having 1 to 3 carbon atoms. Further, these alkyl groups may have a carboxylic acid group, a phosphoric acid group, a sulfonic acid group, or a hydroxyl group.

R 'represents an alkoxy group, an alkyl group or an aryl group. The alkyl group and the aryl group of R ₁ , R ₂ and R ′ include those having a substituent, and R ₁ and R ₂
May combine to form a ring, for example, a heterocyclic ring such as piperidine, pyridine, triazine or morpholine.

[0163]

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In the formula, R ₁₁ , R ₁₂ and R ₁₃ represent a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group or a heterocyclic group, and R ₁₄ represents a hydroxy group, a hydroxyamino group, a substituted or unsubstituted group. Represents a substituted alkyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, carbamoyl group, or amino group. The heterocyclic group is a 5- to 6-membered ring and is composed of C, H, O, N, S and a halogen atom, and may be saturated or unsaturated. R ₁₅ is -CO-, -SO ₂
-Or

[0165]

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And represents a divalent group selected from the group consisting of: In particular, when n = 0, R ₁₄ represents a group selected from an alkyl group, an aryl group, and a heterocyclic group, and R ₁₃ and R ₁₄ may form a heterocyclic group together.

Specific examples of the hydroxylamine compound represented by the general formula [A] are described in US Pat.
Specific examples of compounds which are described in JP-A Nos. 93034 and 3287124 include particularly preferred specific examples of compounds (A-1) to (A-39) described in Japanese Patent Application No. 2-203169, pp. 36-38. And (1) to (53) described on pages 3 to 6 of JP-A-3-33845 and (1) to (5) described on pages 5 to 7 of JP-A-3-63646.
2).

Next, specific examples of the compound represented by the general formula [B] include (B-1) to (B-33) described in Japanese Patent Application No. 2-203169, pp. 40-43, and JP-A. (1) to (56) described on pages 4 to 6 of the specification of JP-A-3-33846.

The compounds represented by the general formula [A] or [B] are usually free amines, hydrochlorides, sulfates,
It is used in the form of p-toluenesulfonate, oxalate, phosphate, acetate and the like.

In the color developer and black-and-white developer used in the present invention, a trace amount of sulfite can be used as a preservative. Examples of the sulfite include sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, and the like.

It is necessary to use a buffer for the color developing agent and the black-and-white developer used in the present invention. Examples of the buffer include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate and trisodium phosphate. , Tripotassium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (borate), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate And sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate), and the like.

As development accelerators, there are JP-B-37-16088,
37-5987, 38-7826, 44-12380, 45-9019
And thioether compounds represented by U.S. Pat.No. 3,813,247, disclosed in JP-A-52-49829 and JP-A-50-15554.
p-phenylenediamine-based compound, JP-A-50-137726,
JP-B-44-30074, JP-A-56-156826 and JP-A-52-43429
Quaternary ammonium salts represented by US Pat.
P-aminophenols described in Nos. 2 and 4119462, U.S. Pat.Nos. 2,494903, 3,128,182, 4,230,796, and 3,523,919
No., JP-B-41-11431, U.S. Pat.Nos. 2,482,546, and 2596926
No. 3 and No. 3852346, the amine-based compounds described in
7-16088, 42-25201, U.S. Pat.
Polyalkylene oxide represented by 41-11431, 42-23883 and U.S. Pat.
-3-Pyrazolidones, hydrozines, mesoionic compounds, ionic compounds, imidazoles, and the like can be added as necessary.

The color developing agent preferably does not substantially contain benzyl alcohol. Substantially means not more than 2.0 ml, more preferably not containing any, at all in terms of 1 liter of color developer. The one containing substantially no phthalocyanine reduces fluctuations in photographic properties during continuous processing, particularly an increase in stain, and can provide more preferable results.

For the purpose of preventing fog and the like, chlorine ions and bromine ions are required in the color developer in the processing tank. In the present invention, from the viewpoints of fluctuations in development speed, stain, and minimum density, preferably 1.0 × 10 ^{-2 to} 1.5 × 10 ^-1 mol / l, more preferably 4 × 10 ^-2 to 1 × 10 ^-1 as chloride ions. Mol / l. Therefore, the solid processing agent is preferably adjusted so that the color developer in the processing tank is in the above-mentioned concentration range.

In the present invention, the color developer in the processing tank preferably contains bromide ions in an amount of 3.0 × 10 ^{−3 to} 1.0 × 10 ⁻³ mol / l in view of the developing speed, the maximum density, the sensitivity and the minimum density. More preferably, it is from 5.0 × 10 ^{−3 to} 5 × 10 ⁻⁴ mol / l. Particularly preferred is 1 × 10 ^{-4 to} 3 × 10 ^-4 mol / l. It is preferable that the concentration of bromine in the solid processing agent is adjusted to be in the above range, similarly to the case of chlorine ions.

When directly added to a color developing agent, sodium chloride, potassium chloride,
Ammonium chloride, nickel chloride, magnesium chloride,
Manganese chloride, calcium chloride, and cadmium chloride are mentioned, and preferred are sodium chloride and potassium chloride.

The color developing agent and the fluorescent whitening agent added to the developing agent may be supplied in the form of a counter salt. As bromine ion supply substances, sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide, magnesium bromide, manganese bromide, nickel bromide,
Cadmium bromide, cerium bromide and thallium bromide are preferred, of which potassium bromide and sodium bromide are preferred.

The color developing agent and the developer used in the present invention may optionally contain an antifoggant in addition to chlorine ions and bromine ions. As antifoggants, alkali metal halides such as potassium iodide and organic antifoggants can be used. As organic antifoggants, for example, benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, Nitrogen-containing heterocyclic compounds such as 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine and adenine can be mentioned as typical examples.

It is preferable that a triazinylstilbene-based fluorescent whitening agent is contained in the color developer and the developer used in the present invention from the viewpoint of the effects of the present invention. As such a fluorescent whitening agent, a compound represented by the following general formula [E] is preferable.

[0180]

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In the above formula, X ₂ , X ₃ , Y ₁ and Y ₂ each represent a hydroxyl group, a halogen atom such as chlorine or bromine, an alkyl group, an aryl group,

[0182]

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[0183] or an -OR _25. Where R ₂₁ and R ₂₂
Represents a hydrogen atom, an alkyl group (including a substituent) or an aryl group (including a substituent), R ₂₃ and R _{24 each} represent an alkylene group (including a substituent), and R ₂₅ represents a hydrogen atom, an alkyl group (including a substituent). Represents a substituent) or an aryl group (including a substituent), and M represents a cation.

The details of each group of the general formula [E] or the substituents thereof are the same as those described in Japanese Patent Application No. 2-240400, from page 63, bottom line, line 8 to page 64, bottom line, line 3. It is.

Specific examples of the compound represented by formula [E] are shown below.

[0186]

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[0187]

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[0188]

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[0189]

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[0190]

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[0191]

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The above compounds can be synthesized by known methods. Particularly preferred among the above exemplified compounds are E-4, E-24, E-34, E-35, E-36 and E-.
37, E-41. The amount of these compounds to be added is preferably adjusted to a range of 0.2 g to 10 g per liter of the color developing solution, and more preferably from 0.4 g to 5 g.

Further, the color developer and the black-and-white developer composition used in the present invention may contain, if necessary, methylcellosolve, methanol, acetone, dimethylformamide,
β-cyclodextrin, other JP-B-47-33378,
The compounds described in JP-A-44-9509 can be used as an organic solvent for increasing the solubility of a developing agent.

Further, an auxiliary developer can be used together with the developing agent. As these auxiliary developers, for example, metol, phenidone, N, N-diethyl-p-aminophenol hydrochloride, N, N, N ′, N′-tetramethyl-p-phenylenediamine hydrochloride and the like are known. I have.

Furthermore, various additives such as a stain inhibitor, an anti-sludge agent, and a layering effect promoter can be used.

The color developer and the black-and-white developer composition include the following general formula [K] described in Japanese Patent Application No. 2-240400, from page 63, bottom line, line 8 to page 64, bottom line, line 3. It is preferred from the viewpoint of effectively achieving the object of the present invention that a chelating agent represented by the following formula and the exemplified compounds K-1 to K-22 are added.

[0197]

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Among these chelating agents, K
-2, K-9, K-12, K-13, K-17, and K-19 are preferably used, and particularly, K-2 and K-9 exhibit excellent effects of the present invention.

The amount of the chelating agent to be added is preferably 0.1 to 20 g per liter of the color developing solution and 1 g of the black and white developing solution, and more preferably 0.2 to 20 g.
８8 g.

Further, the color developer and the black-and-white developer may contain anionic, cationic, amphoteric and nonionic surfactants.

Further, if necessary, alkyl sulfonic acid,
Various surfactants such as arylsulfonic acid, aliphatic carboxylic acid, and aromatic carboxylic acid may be added.

The bleaching agent preferably used in the bleaching agent or bleach-fixing agent according to the present invention is a ferric complex salt of an organic acid represented by the following general formula [C].

[0203]

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[In the formula, A _{1 to} A ₄ may be the same or different and represent —CH ₂ OH, —COOM, or —PO ₃ M ₁ M ₂ . M,
M ₁ and M ₂ each represent a hydrogen atom, an alkali metal or ammonium. X represents a substituted or unsubstituted alkylene group having 3 to 6 carbon atoms. Hereinafter, the compound represented by the general formula [C] will be described in detail.

In the above formula, A _{1 to} A ₄ are as described in Japanese Patent Application No. 1-260628.
Since the from the page 15, line 15 page on the same meaning as line 3 A ₁ to A ₄ according omit the detailed description.

The ferric complex salt of an organic acid represented by the general formula [C] has a high bleaching ability, so that only a small amount of the ferric complex salt can be used when solidifying, and the solidification of weight reduction and miniaturization can be measured. And has the effect of improving the preservability of the solidifying agent, and is preferably used in the present invention.

Preferred specific examples of the compound represented by the general formula [C] are shown below.

[0208]

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[0209]

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As the ferric complex salts of the compounds (C-1) to (C-12), sodium, potassium or ammonium salts of these ferric complex salts can be arbitrarily used. From the viewpoint of the effect and solubility of the object of the present invention,
Ammonium salts of these ferric complex salts are preferably used.

Among the above compound examples, those particularly preferably used in the present invention include (C-1), (C-3),
(C-4), (C-5) and (C-9), and particularly preferred is (C-1).

In the bleaching agent or the bleach-fixing agent of the present invention, besides the iron complex salt of the compound represented by the general formula [C], a ferric complex salt of the following compound can be used as a bleaching agent.

[A'-1] Ethylenediaminetetraacetic acid [A'-2] Trans-1,2-cyclohexanediaminetetraacetic acid [A'-3] Dihydroxyethylglycinic acid [A'-4] Ethylenediaminetetrakismethylenephosphonic acid [A'-4] A'-5] Nitrilotrismethylene phosphonic acid [A'-6] Diethylenetriamine pentakismethylenephosphonic acid [A'-7] Diethylenetriaminepentaacetic acid [A'-8] Ethylenediamine diorthohydroxyphenylacetic acid [A'-9] Hydroxy Ethylethylenediaminetriacetic acid [A'-10] Ethylenediaminedipropionic acid [A'-11] Ethylenediaminediacetic acid [A'-12] Hydroxyethyliminodiacetic acid [A'-13] Nitrilotriacetic acid [A'-14] Nitrilotri Propionic acid [A'-15] triethylene Tetramine hexaacetic acid [A'-16] Ethylenediaminetetrapropionic acid [A'-17] β-alanine diacetic acid The addition amount of the organic acid ferric complex is 0.01 mol to 2.0 mol per liter of the bleaching solution or the bleach-fixing solution. It is preferably contained, more preferably in the range of 0.05 to 1.5 mol / l. Accordingly, the solid processing agent is preferably adjusted so that the concentration of the organic acid ferric complex in the bleaching solution or the bleach-fixing solution in the processing tank falls within the above range.

Examples of the bleaching agent, the bleach-fixing agent and the fixing agent include imidazole and derivatives thereof described in JP-A-64-295258 and compounds represented by formulas [I] to [IX] described in the same specification. In addition, by containing at least one of these exemplified compounds, an effect on rapidity can be obtained.

In addition to the above-mentioned accelerators, exemplified compounds described on pages 51 to 115 of JP-A-62-123459 and pages 22 to 25 of JP-A-63-17445. And the compounds described in JP-A-53-95630 and JP-A-53-28426 can be used in the same manner.

The bleaching agent or bleach-fixing agent may contain, in addition to the above, halides such as ammonium bromide, potassium bromide and sodium bromide, various optical brighteners, defoamers and surfactants. it can.

As the fixing agent used in the fixing agent or the bleach-fixing agent in the present invention, thiocyanates and thiosulfates are preferably used. The content of the thiocyanate is preferably at least 0.1 mol / l or more per liter of the fixing solution or the bleach-fixing solution, and more preferably 0.5 mol / l or more, particularly preferably, when processing a color negative film.
1.0 mol / l or more. The thiosulfate content is preferably at least 0.2 mol / l or more, and more preferably 0.5 mol / l or more when a color negative film is processed. In the present invention, the object of the present invention can be more effectively achieved by using a combination of a thiocyanate and a thiosulfate.

The fixing agent or the bleach-fixing agent used in the present invention may contain, alone or two or more kinds of pH buffers comprising various salts, in addition to these fixing agents. Further, it is desirable to contain a large amount of a rehalogenating agent such as an alkali halide or an ammonium halide, for example, potassium bromide, sodium bromide, sodium chloride, ammonium bromide and the like. Compounds known to be added to ordinary fixing agents or bleach-fixing agents, such as alkylamines and polyethylene oxides, can be added as appropriate.

A fixing agent or a bleach-fixing agent is described in JP-A-64-2.
It is preferable to add a compound represented by the following general formula [FA] described on page 56 of JP-A-95258 and this exemplified compound, which not only exerts the effects of the present invention better but also allows a small amount of photosensitive material to be used for a long period of time. Another effect is that the amount of sludge generated in the processing solution having a fixing ability when processing over a long period is extremely small.

[0220]

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The compound represented by the formula [FA] described in the same specification is disclosed in US Pat. No. 3,335,161 and US Pat. No. 3,260,718.
It can be synthesized by a general method as described in the specification. These compounds represented by the general formula [FA] may be used alone or in combination of two or more.

The addition amount of the compound represented by the general formula [FA] is 0.1 g to 20 g per liter of the fixing solution or the bleach-fixing solution.
Good results are obtained in the range of 0 g.

In the present invention, the stabilizer preferably contains a chelating agent having a chelate stability constant of 8 or more for ferric ions. Here, the chelate stability constant is described by LGSillen / AEMartell, “Stability Constan
ts of Metal-ion Complexes ”, The Chemical Society,
London (1964). "Organi" by S. Chaberek / AEMartell
c Sequestering Agents ”, mean constants generally known by Wiley (1959) and the like.

As chelating agents having a chelate stability constant for ferric ion of 8 or more, Japanese Patent Application No. 2-234776,
No. 1-324507 and the like.

The above chelating agent was used in an amount of 1 l of the stabilizing solution.
Good results are obtained in the range of preferably 0.01 to 50 g, more preferably 0.05 to 20 g.

Preferred compounds to be added to the stabilizing solution include ammonium compounds. These are supplied by ammonium salts of various inorganic compounds. The addition amount of the ammonium compound is preferably in the range of 0.001 mol to 1.0 mol per liter of the stabilizing solution, more preferably 0.002 to 2.
It is in the range of 0 mol.

Further, the stabilizer preferably contains a sulfite.

Further, the stabilizer preferably contains a metal salt in combination with the chelating agent. As such metal salts, Ba, Ca, Ce, Co, In, La, Mn, Ni, Bi, Pb,
There are metal salts of Sn, Zn, Ti, Zr, Mg, Al or Sr, which can be supplied as inorganic salts such as halides, hydroxides, sulfates, carbonates, phosphates, acetates or water-soluble chelating agents. . The amount used is preferably in the range of 1 × 10 ^-4 to 1 × 10 ^-1 mol, more preferably in the range of 4 × 10 ^-4 to 2 × 10 ^-2 mol per liter of the stabilizing solution.

[0229]

【Example】

(Embodiment 1) An example of an automatic developing machine to which the present invention can be applied (hereinafter simply referred to as an automatic developing machine) will be described with reference to the drawings. FIG. 1 is a schematic diagram of a printer processor in which a self-developing machine A and a photographic printer B are integrally configured.

In FIG. 1, a magazine M containing rolls of photographic paper, which is an unexposed silver halide photographic material, is set in the lower left portion of the photographic printing apparatus B. The photographic paper pulled out of the magazine is cut into a predetermined size via the feed roller R and the cutter unit C, and becomes a sheet-like photographic paper. This sheet-shaped photographic paper is transported by the belt transport means B, and the image of the original O is exposed at the exposure section E. The exposed sheet-shaped photographic 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-like photographic paper is processed by a color developing tank 1A, a bleach-fixing tank 1B, and stabilizing tanks 1C, 1D, 1 which are processing tanks, respectively.
The inside of E (consisting essentially of three tanks) is successively conveyed by roller conveying means (reference symbol pear), and subjected to a color developing process, a bleach-fixing process, and a stabilizing process, respectively. The sheet-shaped photographic paper subjected to each of the above processes is dried in the drying unit 35 and discharged outside the machine.

The dashed line in the figure indicates the transport route of the silver halide photographic material. Further, in the embodiments, the photosensitive material is guided into the automatic processing machine A in a cut state, but may be guided into the automatic processing machine in a belt shape. In this case, if an accumulator for temporarily storing the photosensitive material is provided between the automatic developing machine A and the photographic printing machine B, the processing efficiency is increased. Further, it goes without saying that the self-developing machine according to the present invention may be configured integrally with the photoprinting machine B, or may be a single self-developing machine. Further, the silver halide photographic light-sensitive material processed by the self-developing machine according to the present invention is not limited to an exposed photographic paper, and it goes without saying that an exposed negative film or the like may be used. Further, as an explanation of the present invention, an automatic developing machine having a substantially three-tank configuration having a color developing tank, a bleach-fixing tank, and a stabilizing tank will be described. However, the present invention is not limited thereto. The present invention can be applied to an automatic developing machine having a substantially four-tank configuration having a tank and a stabilizing tank.

FIG. 2 is a sectional view of the color developing tank 1A which is a processing tank in the II section of the automatic processing 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 It is assumed here that all of the tanks 1C, 1D and 1E are pointed out.

[0233] In the figure, a conveying means for conveying the photosensitive material is omitted for easy understanding of the configuration.
Further, in this example, a case where the tablet 13 is used as the solid processing agent will be described.

A processing tank 1 is provided with a processing section 2 for processing a photosensitive material.
And a solid processing agent supply section 11 for supplying a tablet 13 integrally provided outside a partition wall forming the processing section. The processing section 2 and the solid processing agent charging section 11 are separated by a partition wall 12 having a communication window, so that the processing liquid can be circulated. Since the charging section 11 is provided with the section 14 for receiving the processing agent, it does not move to the processing section 12 as a solid.

[0235] The cylindrical filter 3 is provided with a solid processing agent charging section.
It is replaceably provided below 11 and has a function of removing insoluble matter in the processing liquid, for example, paper waste. In the filter 3, a circulation pump 5 (circulation means) is provided via a circulation pipe 4 provided through the lower wall of the solid processing agent introduction section 11.
Is connected to the suction side.

The circulation system is constituted by the circulation pipe 4 forming the circulation path of the liquid, the circulation pump 5, the treatment tank 1, and the like. The other end of the circulation pipe 4 communicating with the discharge side of the circulation pump 5 penetrates a lower wall of the processing unit 2 and communicates with the processing unit 2. With such a configuration, when the circulating pump 5 is operated, the processing liquid is sucked from the solid processing agent charging section 11, discharged to the processing section 2, mixed with the processing liquid in the processing section 2, and solid processing agent is returned again. The circulation entering the charging section 11 is repeated. The flow rate of this circulation flow is 1
The flow rate is preferably 0.1 (rotation = circulation amount / tank capacity) or more with respect to the tank capacity per minute, more preferably 0.5 to 2.0 rotations. Further, the circulation direction of the processing liquid does not need to be 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 level at a constant level. Ingredients leaching from the material are stored,
Help prevent increase.

The rod-shaped heater 7 is arranged so as to penetrate the upper wall of the solid processing agent charging section 11 and to be immersed in the processing liquid in the solid processing agent charging section 11. The heater 7 is provided in the processing tank 1
To heat the processing solution in the tank, in other words, the processing tank 1
Temperature range suitable for processing the processing solution inside (for example, 20 to 55 ° C)
Is a temperature adjusting means for holding the temperature.

The processing amount information detecting means 8 is provided at the entrance of the automatic processing 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 counting the detected time. Since the conveying speed of the photosensitive material is mechanically set in advance, 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 means that can detect the width and the transport time of the photosensitive material, such as an infrared sensor, a microswitch, and an ultrasonic sensor.

In the case where the processing area of the photosensitive material can be indirectly detected, for example, in the case of a printer processor as shown in FIG. 1, the amount of the photosensitive material subjected to printing or the photosensitive material having a predetermined area is determined. The number of processes may be detected. Further, the detection timing is before the processing in this example, but may be after the processing or during the immersion 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). Furthermore, as information to be detected, in the above description, the processing area of the photosensitive material has been described. However, the present invention is not limited to this, and the processing amount of the photosensitive material to be processed, processed, or being processed is not limited thereto. Any value may be used as long as it is a proportional value, and may be a concentration or a change in concentration of the processing liquid stored in the processing tank. Further, the processing amount information detecting means 8
It is not necessary to provide each processing tank 1A, 1B, 1C, 1D, 1E, and it is preferable to provide one for each automatic processing machine.

The processing agent supply means 17 for charging the solid processing agent stored in the cartridge 15 as the storage means into the processing tank is
It has a cartridge 15 in which a tablet 13 which is a solid processing agent is sealed, and an extruding member 10 configured to extrude one or a plurality of tablets 13, which is disposed above a filtration unit (section) 14. This processing agent supply means 17 is provided with a processing agent supply control means 9 described later.
In response to the supply signal issued from the processing agent supply control means 9, the tablet 13 which has been on standby is pushed out by the extruding member 10, and the tablet 13 is filtered (separated) in the solid processing agent input section 11. Supply 14

In the present invention, the solid processing agent 13 is supplied to the filtration section (section) 14 in the solid processing agent receiving section 11. In other words, in the present invention, it is sufficient that the solid processing agent can be dissolved using the processing liquid, and the components corresponding to the processing amount information of the photosensitive material are surely charged, and the processing characteristics of the processing liquid in the processing tank 1 are kept constant. Although it is necessary, it is more preferable that the solid processing agent is supplied into the circulation path of the processing liquid. Further, the processing agent supply means 17 is configured to prevent the inside of the processing tank of the automatic processing machine, the humidity of the outside air, and the scattered processing liquid from coming into contact with the solid processing agent before being supplied to the processing tank. Is preferred.

The filtering means (section) 14 is a solid processing agent input section.
Insoluble components by the tablet 13 immersed in the processing liquid in 11, and supplied by the processing agent supply means 17, for example, an insoluble component mixed in the tablet 13, a tablet formed by disintegration of the tablet 13.
13 Removes not only tablets 13 but also tablets 13 as well as those originating from solid processing agents that adhere to the photosensitive material, resulting in images 12 that can cause scratches or cause insufficient processing of the adhered parts. It is. This filtering means (section) 14 is processed with resin. It is not essential that the filtering means (section) 14 be provided in the solid processing agent supply unit 11, and the tablets 13 supplied by the processing agent supply unit 17 are used for transporting the photosensitive material shown in FIG. What is necessary is just to make it inject | pour into the processing liquid in 2.

The processing agent supply control means 9 comprises 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 supply means 17. It emits. Note that the processing agent supply control means 9 may control the processing agent supply means 17 so as to supply the required processing agent amount to the solid processing agent input unit 11 according to the processing amount information.

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 accumulation of the 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. Emits. Upon receiving the supply signal, the processing agent supply means 17 pushes out the tablets 13 with the extruding member 10 and supplies the tablets 13 to the filtering means (section) 14 in the solid processing agent introduction section 11.
The supplied tablet 13 is dissolved by the processing liquid in the solid processing agent charging section 11, but is circulated by the circulating means.
The dissolution is promoted by the treatment liquid circulating from 11 → circulation pump 5 → treatment section 2 → communication window → solid treatment agent introduction section 11. On the other hand, the detected photosensitive material is sequentially conveyed in the color developing tank 1A, the bleach-fixing tank 1B, and the stabilizing tanks 1C, 1D, and 1E by roller conveying means (see the automatic developing machine A in FIG. 1). The processing agent supply means 17 may be provided in each of the processing tanks, ie, the color developing tank 1A, the bleach-fix tank 1B, and the stabilizing tanks 1C, 1D, and 1E, and may be supplied simultaneously. Further, the timings of supply by the respective supply means may be different from each other. Further, a predetermined area for controlling the treatment agent supply means by the treatment agent supply control means 9 is equal to each processing tank 1.
A, 1B, 1C, 1D, and 1E may be the same, but needless to say, they may be different.

In the present invention, a commercially available dehumidifier is operated as a water-in-gas separation device (not shown) so as to be in the vicinity of the automatic developing machine, in particular, the solid processing agent storage means 15 and the processing agent supply device. The means 17 is configured to be dried in the vicinity thereof, so that it is possible to prevent the tablets 13 from joining each other.

The operation timing of the dehumidifier can be determined according to the conditions such as the humidity and temperature of the outside air. In a high humidity condition such as summer, regardless of whether the automatic developing machine is operated. , It is possible to keep it running all day.

On the other hand, when the surrounding environment is low in humidity, it is possible to perform the operation while appropriately humidifying using a humidifier generally commercially available from a nearby water supply source.

Not only in this example but also in the following example,
In the bleach-fix tank 1B and the stabilization tanks 1C, 1D, 1E,
Since the structure is the same as that of the color developing tank 1A, the processing tank 1 is described below.
In this case, the color developing tank 1A, the bleach-fixing tank 1
B, here refers to any of the stabilization tanks 1C, 1D, 1E,
In the figure, those having the same functions as those in FIG. 2 are denoted by the same reference numerals, and the description thereof will be omitted here. Is omitted. Although the filtering means is described as a preferred example in the present embodiment, the effects of the present invention can be sufficiently achieved without the filtering means in the present invention.

As described above, according to the present invention, the replenishment tank which was conventionally required becomes unnecessary and the space for the replenishment tank is not required, so that the automatic processing machine becomes compact, and the solid processing agent is supplied to the processing tank. Since the liquid is supplied, there is no need for liquid preparation work, there is no liquid splashing at the time of liquid preparation, and there is no attachment or contamination to the human body, clothes, or peripheral equipment, and handling is easy.
The replenishment accuracy of the processing solution is improved, and the replenished processing components are not deteriorated and the solid processing agent has stable processing characteristics without deterioration itself.

Next, as another example of the present invention, FIG. 3 is a cross-sectional view of the color developing tank 1A taken along the line II of the self-developing machine A in FIG. FIG. 4 is a cross-sectional view of a part with a processing agent supply unit. FIG. 4 shows the automatic machine A of FIG.
FIG. 3 is a schematic plan view showing the water replenishing means from the top (however, the path of the water replenishing means is described for the sake of explanation). FIG. 5 is a block diagram related to control according to the present example. FIG. 6 is a block diagram in which the evaporation rehydration setting means 23 programmed in advance is added to the control means. FIGS. 3 and 4 show a refill tank 43 for storing replenishment water. In this example, a case where a tablet is used as the solid processing agent 13 will be described.

First, portions different from FIG. 2 in FIGS. 3 and 4 will be described.

The replenishing water supply means 42 is a means for replenishing replenishing water (replenishing water) from the replenishing water tank 43 for storing the replenishing water to the treatment agent receiving portion 11, and includes a hot water replenishing device 32 comprising a pump, a temperature controller and the like. , A solenoid valve 33 and a water supply pipe 36. The replenishment water supply means 42 is for supplementing the water taken out by the photographic material and the water evaporated from the tank surface, while diluting the accumulation suppressing component eluted by the reaction. A rehydration tank or a rehydration pump may be provided for each of the treatment tanks 1A, 1B, 1C, 1D, and 1E. In this case, the automatic generator becomes compact, and more preferably, only one rehydration tank and rehydration pump are provided in the automatic generator,
Provide a solenoid valve in the refilling path (pipe, etc.) to supply the required amount to each treatment tank when necessary, or adjust the replenishment amount by adjusting the diameter of the water supply pipe By doing so, only one water refill tank 43 and one water refill pump can be provided in the self-developing machine, resulting in further compactness. In addition, for the stabilizing tanks 1C and 1D, which are processing tanks, respectively, by supplying the overflowing stabilizing liquid from the stabilizing tanks 1D and 1E, the replenishing water supply means can be omitted. Further, it is preferable that the temperature of the replenishing water in the water refilling tank is controlled.

Reference numeral 960 denotes a commercially available dehumidifier used as a device for separating moisture in gas. The dehumidifier 960 is configured to dehumidify the air taken in from the intake duct 963 and to dry the vicinity of the automatic developing machine. Meanwhile, dehumidifier
The water condensed by the 960 is supplied to the tank 43 for make-up water.
And used as replenishing water by the means.
Further, the replenishment tank 43 is configured to be able to replenish the insufficient replenishment water 961 from outside the automatic developing machine. However, in the present invention, the replenishment of the replenishment water 961 is sufficiently reduced.

The water replenished as a shortage is not only general water such as well water or tap water, but also isothiazoline-based water.
Known compounds that do not affect photographic performance, such as those containing an antifungal agent such as a chlorine-releasing compound or a small amount of a sulfite chelating agent, such as those containing ammonia or inorganic salts,
A method can be used. .

The replenishment water control means controls the replenishment water supply means 42 by the evaporative replenishment setting means 23 programmed in advance according to the environmental temperature and humidity (relative humidity) at the installation location, and / or the processing amount information detection means. 8 is a control means for controlling the replenishment water supply means 42 in accordance with the processing amount information and the like detected by 8. The replenishing water supply control unit is not limited to responding to the processing amount information detected by the processing amount information detecting unit 8, and controls the replenishing water supply in accordance with the information that the processing agent is supplied by the processing agent supply unit 17. Is also good.

The functions and the like of the different parts between FIG. 3 and FIG. 2 other than the above are the same as those in FIG.
It will be described.

The heater 7 is disposed at the bottom of the processing section 2 and heats the processing liquid in the processing section 2. In other words, the heater 7 heats the processing liquid in the processing section 2 and the solid processing agent charging section 11. It performs a temperature control function of maintaining a temperature range suitable for processing (for example, 20 to 55 ° C.).

As the circulating means, a circulating pipe 4 and a circulating pump 5 are provided in the same manner as in FIG. 2, but the difference from FIG. 2 is that the processing liquid circulates in the opposite direction. Part 2 → Circulation pump 5 → Solid processing agent input part 11 →
It circulates from the communication window to the processing unit 2.

The processing agent supply means 17 supplies the tablet 13, which is a solidification processing agent, enclosed in the cartridge 15 to the filtration section (section) 14 in the solid processing agent introduction section 11 by a pushing claw 18. . 2 differs from FIG. 2 in that the cam 19 is actuated by a single rotation stop mechanism, the push claw 18 is actuated, and the tablets 13 that have been on standby are supplied to the processing tank 1, and the next tablets 13 Since the spring is urged downward from above by 21, the standby state is quickly established. At this time, the treatment agent supply means 17 may be of a horizontal type or a push-up type from below, and it is essential that the treatment agent supply means 17 be a means capable of supplying the solid treatment agent to the treatment tank 1.

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

The automatic processing machine including various processing tanks has been described above. The processing tanks include a developing tank for storing a developing solution, a bleaching tank for storing a fixing solution, and a bleaching tank for storing 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 storing unit and / or the fixing unit, the supply unit, and the control unit are each An automatic developing machine for a color negative film provided for each processing tank and a processing tank for storing a developing solution and a fixing tank for storing a fixing solution, and at least the storage means and / or The effects of the present invention were also recognized with respect to an automatic developing machine for a black-and-white silver halide photographic light-sensitive material in which the fixing means, the supply means and the control means were provided for each of the processing tanks.

FIG. 7 is a schematic diagram showing another embodiment of the automatic developing machine according to the present invention. The processing apparatus shown in FIG.
The apparatus has the same structure as the apparatus shown in FIG. 4 except that the air dehumidified by the dehumidifier 960 is sent to the solid processing agent supply means 17 to further prevent the moisture absorption. Reference numeral 962 denotes a duct for sending the dehumidified air to the solid processing agent supply means 17.

FIG. 8 shows the solid processing agent supply means in FIG.
It is a schematic structure figure showing the example of 17a. 3 is the same as the apparatus shown in FIG. 3 except that the solid processing agent 13 is dried by sending dry air 962A generated from the dehumidifier 960 to the solid processing agent supply means 17a shown in FIG. It is. The introduced air is exhausted from the exhaust port.
The amount of the dry air 162A to be sent depends on the solid processing agent supply means 17.
It is possible to adjust by measuring the humidity in a. With such a configuration, deterioration of the solid processing agent 13 accommodated in the solid processing agent supply means 17a due to moisture can be extremely reduced.

The operation of the dehumidifier 960 is most efficiently performed by detecting the humidity inside the solid processing agent supply means 17a and operating it. Such control is performed.

FIG. 9 is a schematic diagram showing another embodiment of the automatic developing machine according to the present invention. This apparatus shows an example having means for separating moisture by inhaling steam discharged from a drying unit of a processing apparatus. The device shown in FIG.
It has the same mechanism as the processing apparatus shown in FIG. 5 except that the suction section of the dehumidifier 960 and the exhaust section of the drying section 35 of the processing apparatus are communicated with each other through a duct 964. The operation timing of the dehumidifier 960 is such that water can be obtained most efficiently when the inside of the drying unit 35 is at high humidity, that is, when the processing apparatus (automatic developing machine) is operating. It is controlled to operate in conjunction with driving.

FIG. 10 is a schematic structural view showing another embodiment of the automatic developing machine according to the present invention. This apparatus shows an example having means for separating moisture by inhaling steam existing in the upper part of the processing tank of the processing apparatus. The apparatus shown in the same drawing has the same mechanism as that of the processing apparatus shown in FIG. 4 except that an intake section of the dehumidifier 960 and an exhaust section for exhausting steam on each processing tank of the processing apparatus are communicated by a duct 965. have.

The operation timing of the dehumidifier 960 is such that water is obtained most efficiently when the inside of each of the processing tanks 1A to 1E is at high humidity, that is, when the processing apparatus (automatic developing machine) is operating. Therefore, it is controlled to operate in conjunction with the operation of the processing device.

FIG. 11 is a schematic diagram showing still another embodiment of the automatic developing machine according to the present invention. This apparatus shows an example having a means for separating moisture by inhaling gas exhausted from a solid processing agent supply means. The device shown in the figure is an intake part of the dehumidifier 960 and the solid processing agent supply device 1.
Fig. 7 except that the exhaust port of 7a is communicated with duct 966.
Has the same mechanism as the processing apparatus shown in FIG.

The dehumidifier 960 used in this embodiment is as follows.

As a heat pump type dehumidifier, Sanyo Electric Co., Ltd.
A dehumidifier SAD-140R (dehumidification capacity: 12 l / day) manufactured by Co., Ltd. was modified and used in accordance with this example.

Even when the dehumidifier using the Peltier element was modified and used, almost the same effect could be obtained. FIG. 12 shows a schematic configuration of the dehumidifier.
In the figure, 1200 is an air intake, 1201 is a passage through which air passes, 1202 is an outlet for dry air, 1203 is a condenser composed of a Peltier element, 1203A is a cooling surface, 1203B
Is the heating surface. 1204 is a pipe for guiding the concentrated liquid to the tank 43. A bismuth tellurium alloy was used as a metal or semiconductor used for the Peltier device.

Also, substantially the same effect could be obtained when a modified dehumidifier using a semipermeable membrane for separating moisture was used. As the dehumidifier using the semipermeable membrane, one having a structure shown in FIG. 13 was used. In the figure,
Reference numeral 1210 denotes a membrane module. A plurality of polyimide hollow fiber membranes (UBE Komyo Co., Ltd. UBE membrane dryer UM-A1) composed of a polyimide membrane which is a semipermeable membrane that separates moisture are installed in the outer cylinder 1211 in the vertical direction. Are located in 12
12 is a dust removal filter for air to be dehumidified, 1213 is an inlet for air to be dehumidified, 1214 is an outlet for dehumidified air, 1215 is an air supply port to the shell side, 1216 is an outlet for humid air,
The high-humidity air discharged from the discharge port 1216 was introduced into the dehumidifier using the Peltier device described above, so that dry air and a concentrated liquid were obtained.

(Example 2) Tables 1, 2 and 3 show the kit forms of conventional treatment agents.

[0275]

[Table 1]

[0276]

[Table 2]

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

[0278]

[Table 3]

Tables 4, 5 and 6 show the forms of the treating agents of the present invention.
Shown in

[0280]

[Table 4]

[0281]

[Table 5]

In the table, EDTA-Fe salt represents ferric ammonium ethylenediaminetetraacetate.

[0283]

[Table 6]

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

[0285]

[Table 7]

[0286]

[Table 8]

Here, the processing agent for color paper will be described as an example. In the conventional treating agent, each additive material is concentrated in a liquid part for the purpose of simplifying the dissolving operation at a minilab installation store. In such a case, several types of parts are made by combining materials that are stable for a long period of time.

[0288] These kits are limited to the original solubility of the chemical no matter how thick the kit is, and water is added in addition to the essential chemicals.

In particular, mixing unnecessary water means carrying water in an extreme case, which increases the load on transportation costs.

In contrast, the treating agent of the present invention is solidified and does not need to be mixed with water at all, so that it can take the form of a treating agent containing only essential chemicals. Therefore Table 1
Comparing Table 3 with Tables 4-6, it is possible to reduce the weight of replenisher to 46% for a color developing replenisher, 23% for a bleach-fix replenisher and 23% for a super stabilizer for the same processing amount of photographic material.

Next, Table 7 shows the characteristics of the treating agent of the present invention. In general, a minilab treating agent, a minilab quick treating agent, and a large laboratory treating agent have a part configuration as shown in Table 7. .

The conventional processing agent is a mini-lab quick processing agent in which the processing agent is dissolved once as a replenisher and replenished in accordance with the processing amount of the light-sensitive material. The density difference is gradually increasing.

There is a limit to increasing the concentration of the replenisher.
The color developing solution is about 1.7 times the tank solution, and the bleach-fix solution (not shown here, but also has the bleaching ability for negative processing) is about 2.2 times the tank solution because of solubility. .

When the replenisher is stored at the above concentration, precipitation of the color developing agent occurs in the replenisher for color development, and precipitation of ferric ethylenediaminetetraacetic acid occurs in the bleach-fixer. It is particularly susceptible to temperature and causes trouble in winter when the temperature around the replenishment tank is 10 ° C or less.

[0295] Further, since the parts of the kit are constituted in consideration of the storage stability of the liquid kit, the pH may be extremely low or extremely high depending on the product. Therefore, the operator has to pay attention to the handling of the kit solution.

[0296] Leakage of kit solution, attachment to clothes,
If it gets on the skin, an unexpected accident will occur. That is, it leaks a kit solution with a low pH or a kit solution with a high pH and rusts when it comes into contact with metal parts, when it gets on clothing, the part is damaged, and when it gets on the skin, the part gets fogged or eczema occurs .

Further, the transportation of the treating agent is subject to legal restrictions.

That is, it is stipulated by UN (United Nations) rules and the like, and must comply with the Ship Safety and Health Law and the Aviation Law. In the case of air transport, there are some parts that must adhere to IATA regulations. In the table, those marked with an X for corrosiveness and transport safety cannot be transported unless they are filled in containers that clear the container inspection etc. of the corresponding kit.

The processing agent of the present invention is solidified and does not need to be dissolved as a replenisher, and can be replenished directly to the tank solution in accordance with the processing amount of the light-sensitive material. Only by increasing the ratio of the consumed components, an advantageous configuration can be taken which is not limited to the solubility, so that there is no concern about troubles such as material deposition.

Further, since the kit form is not liquid, the weight can be reduced and the load on transportation costs can be reduced. In addition, it is not necessary to take into account corrosion resistance and transport safety.

(Example 3) Konica QA paper type A
5 (Konica Corporation) was imagewise exposed, and then the Konica Big Minilab BM-101 (Konica Corporation) was remodeled into the peel open system shown in FIG. Modifications were made and continuous processing was performed.

[0302]

[Table 9]

The stability was a countercurrent system from 3 to 1, and the entire amount of the overflow liquid of Stable-1 was flowed into the bleach-fixing tank. The carryover per 1 m ^{2 of} the photosensitive material was 50 ml / m ² in all the tanks.

In addition, during the temperature control, the color development, bleach-fix, and stably are performed at 9.0 ml / hour, 7.2 ml / hour, and 14.1 ml / hour, respectively, every hour. , 3.8m each
l / h, 3.1 ml / h and 6.1 ml / h were integrated, and the operation was performed at the start of temperature control.

The tank liquid at the start was Konica Color Q
A-paper color development starter 82P-1B, (Konica Color QA paper bleach-fixer starter 82P-2B manufactured by Konica Corporation)
(Same as above), Konica Color QA Paper Stabilizer 82
Created using P-3B (Id.).

A processed tablet for color paper was prepared according to the following operations (A to G).

1) Replenishing tablet for color development for color paper Operation (A) CD-3 [4-amino-3-methyl-N-ethyl-N- [β-
(Methanesulfonamido) ethyl] aniline sulfate] 1200
g is ground in a commercially available bandam mill until the average particle size is 10 μm. After granulating the fine powder in a commercially available stirring granulator at room temperature for about 7 minutes by adding 50 ml of water, the granulated material is dried at 40 ° C. for 2 hours in a fluidized bed drier. Almost completely removes water from the granules. Thus, 150 g of polyethylene glycol 6000 was added to the adjusted granules at 25 ° C and 40 ° C.
Mix evenly for 10 minutes using a mixer in a room humidified below% RH. Next, 4 g of sodium N-lauroylalanine
Was added and mixed for 3 minutes, and the obtained mixture was subjected to compression tableting with a tableting machine modified from Tough Press Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd. to make the filling amount per tablet 3.2 g, to obtain 400 tablets. Replenishing tablet A for color development for color paper
A preparation was made.

Operation (B) Disulfoethylhydroxylamine disodium salt 120 g
Is pulverized and granulated in the same manner as in the operation (A). The amount of water added is 6.
After the granulation, the mixture is dried at 50 ° C. for 30 minutes to almost completely remove the water content of the granulated product. In this manner, N-lauroylalanine sodium 4 was added to the prepared granules,
Mix for 3 minutes using a mixer in a room conditioned at a temperature of 40 ° C. and below 40% RH. Next, the obtained mixture was mixed with a tableting machine obtained by modifying a tough press collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd.
Compression tableting was performed with the filling amount per tablet being 1.0 g to prepare 100 color developing and replenishing tablets B 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 diethylenetriaminepentaacetic acid, 25 g of sodium p-toluenesulfonate
g, 20 g of potassium hydroxide and 10.6 g of mannitol are pulverized in the same manner as in (A), and then uniformly mixed with a commercially available mixer. Next, in the same manner as in (A), granulation is performed with the amount of water added being 20 ml. After the granulation, the granules are dried at 60 ° C. for 30 minutes to almost completely remove the moisture of the granules. In this way, 4 g of N-lauroylalanine sodium was added to the prepared granules,
Using a mixer in a room conditioned at 5 ° C, 40% RH or less
Mix for a minute. Next, the obtained mixture was subjected to compression tableting with a tableting machine modified from Tough Press Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd., with the filling amount per tablet being 1.0 g, and 100 tablets.
A color developing and replenishing tablet C for color paper was 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 to be added is 20 ml, and after granulation, it is dried at 700 ° C. for 30 minutes to almost completely remove water from the granulated material. In this way, polyethylene glycol 6000 is added to the adjusted granules.
15 g is uniformly mixed for 10 minutes using a mixer in a room conditioned at 25 ° C. and 40% RH or less. Next, 4 g of sodium N-lauroylalanine was added and mixed for 3 minutes, and the resulting mixture was tough pre-collect 1527H manufactured by Kikusui Seisakusho Co., Ltd.
U was converted to a tableting machine with a tableting machine modified to make the filling amount per tablet 3.0 g, and compression tableting was performed to prepare 110 color developing and replenishing tablets D for color paper.

2) Tablet for replenishing bleach-fix for color paper Procedure (E) Diethylenetriaminepentaacetic acid ferric ammonium salt monohydrate
1250 g, ethylenediamine tetraacetic acid 25 g, maleic acid 250 g,
46 g of Pine Flow (Matsuya Chemical) is pulverized, mixed and granulated in the same manner as in the operation (C). The addition amount of water is 80 ml, after granulation,
After drying at 60 ° C. for 2 hours, the water content of the granulated material is almost completely removed. 15 g of N-lauroyl sarcosine sodium is added to the thus-prepared granules, and mixed for 3 minutes using a mixer in a room conditioned at 25 ° C. and 40% RH or less. Next, the obtained mixture was compressed and compressed with a tableting machine modified from Tough Press Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd. to a filling amount of 8.6 g per tablet, and bleach-fixing for 170 color papers was replenished. Tablet A 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). Water spray amount is 10
After the granulation, the mixture is dried at 60 ° C. for 120 minutes to almost completely remove the water content of the granulated product. In this way, 20 g of sodium N-lauroyl sarcosine was added to the prepared granules,
Using a mixer in a room conditioned at 5 ° C, 40% RH or less
Mix for a minute. Next, the obtained mixture was subjected to compression tableting using a tableting machine modified from Tough Press Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd., with the filling amount per tablet being 13.4 g, and 180 tablets.
A tablet B for replenishing bleach-fix for color paper was prepared.

3) Tablet for stable replenishment for color paper Operation (G) Sodium carbonate monohydrate 10 g, 1-hydroxyethane-1,1-
Disodium diphosphonate 200g, Tinopearl SFP150
g, sodium sulfite 300 g, zinc sulfate heptahydrate 20 g, ethylenediaminetetraacetic acid disodium 150 g, 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). The amount of water added
After granulation, the mixture is granulated and dried at 70 ° C. for 60 minutes to almost completely remove moisture from the granulated product. In this manner, 10 g of N-lauroyl sarcosine sodium was added to the prepared granules, and 2
Using a mixer in a room conditioned at 5 ° C, 40% RH or less
Mix for a minute. Next, the obtained mixture was subjected to compression tableting with a tableting machine modified from Tough Presto Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd. to make the filling amount per tablet 3.1 g, and 360
Individual tablets for color paper stable replenishment were prepared.

Next, for the tablets for color development and replenishment, the tablets A, B, C, and D were each one tablet, for a total of four tablets, one tablet at a time.
Using a peel-open packaging material, the continuous 20-minute package was packaged by a four-sided sealing method. As for the tablet for replenishing bleach-fixing, one tablet of the agent A and two tablets of the agent B were divided into a total of three tablets in one-minute package, and a continuous 20-minute package was packaged in the same manner as the above-mentioned tablet for replenishing color development.

Further, for tablets for stable replenishment, 1
Each tablet was divided into 1 packet, which was divided in the same manner as described above.

[0316] The peel-open packaging material was prepared by laminating the unstretched polypropylene film / stretched polypropylene film on the unstretched polypropylene film surface using Tocello CMPSO11C as a sealant film.

[0317] The peel open film thus produced and the unstretched polypropylene / stretched polypropylene film were heat-sealed, and the tablets were packaged.

As a comparative example, the present tablet and its corresponding replenishing water were placed in a replenishing tank to prepare a 10-liter replenisher and used.

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

The processing was performed using 5 m ^{2 of} color paper per day until the amount of overflow became twice the amount of the tank liquid. Thereafter, the number of days until sulfidation in the bleach-fix tank was observed, and the sample subjected to wedge exposure was developed. The maximum reflection density of blue was measured.

However, the color developing agent in the color developing agent is as follows:
In replenishment rate 50 ml / m ^2, 1.2-fold 25 ml / m ² is 1.45 times, 150 ml / m
^{In the case of 2} , it was changed to 0.9 times and the consumption was corrected.

The amount of maleic acid in the bleach-fix solution was as follows:
When the replenishment was reduced, the amount was increased by the amount of the increase in pH due to the mixing of the color developing solution. Table 10 shows comparative examples of each method.

[0323]

[Table 10]

Further, the replenishment amount and renewal rate of the replenisher were changed, and continuous processing was performed. The solid processing agent introduction method of the present invention was compared with the conventional replenisher preparation method, and the concentration of the bleach-fix solution was measured. The concentration rate was determined by measuring the concentration of iron ions in the tank liquid by atomic absorption.

Further, the replenisher was dissolved in a color developer to prepare a replenisher, and the dissolution state was observed.

[0326]

[Table 11]

As is clear from Table 11 above, in the conventional replenisher preparation method, when the replenishment was reduced, the replenisher had to be concentrated, and when the replenisher was prepared, the replenisher was not completely dissolved and insoluble matter remained. I will. In addition, when the replenishment rate is low, the replenisher is also oxidized and deteriorated, so that a sufficient density cannot be obtained by measuring the photographic density.

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

Further, in the case of the bleach-fix solution, it was found that the replenisher at the time of low replenishment had a low pH and had poor storage stability, and was sulfurized in several weeks. However, in the method of the present invention, since it is not necessary to prepare a replenisher, sulfurization of the bleach-fixer does not occur at all.

When the concentration of the bleach-fixing solution is measured, the current replenishing solution system causes a large concentration in a low replenishing region. In particular, in a region where the replenishing amount is smaller than the amount of evaporation, the evaporation is corrected using the replenishing solution. The concentration rate increases.

However, in the case of the present invention, since the evaporation correction can be performed separately, no concentration is performed at all, and it is understood that the method is indeed excellent.
FIG. 14 is a characteristic diagram comparing the relationship between the replenishment amount and the enrichment ratio between the prior art and the present invention.

(Example 4) Konica QA paper type-
5 (manufactured by Konica Corporation) after imagewise exposure of the KN-5 (manufactured by Konica Corporation) having the configuration shown in FIG.
Was processed according to the following processing steps. However, the replenishing water in the replenishing tank used was deionized.

Processing step Processing time Processing temperature Tank capacity Color development 22 seconds 38.0 ° C 12l Bleaching and 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 method from 3 to 1, and the entire overflow of Stable-1 was flowed into the bleach-fix tank. The 45ml carryover of the photosensitive material 1 m ² per light-sensitive material from the color developing tank to the bleach-fixing bath, 50m is to stabilizing tank from a bleach-fixing tank
1, 40 ml for stable-1 → 2,2 → 3 and 3 → dry.

The opening area of each of the color developing tank, bleach-fixing tank and stabilizing tank was 4.5 cm ² per liter of processing solution.

The outside air of the self-developing machine was at 27 ° C. and 60% RH, and the replenishing water was replenished when the amount of evaporation reached 100 ml.

The formula for replenishing water was calculated using the equation (1) in JP-A-3-280042. The processed light-sensitive material was processed at 2.0 m ² per day and processed continuously for two months.

The composition of the processing solution is shown below.

(Color developing solution) Potassium bromide 0.02 g Potassium chloride 3.2 g Potassium carbonate 30 g Potassium sulfite 0.2 g Sodium diethylenetriaminepentaacetate 2 g Sodium nitrilotrimethylene phosphonate 2 g Tinopearl SFP 2 g Disodium-N, N-bis (sulfonateethyl Hydroxylamine 5 g 4-Amino-3-methyl-N-ethyl N- [β- (methanesulfonamido) ethyl] aniline sulfate 7 g (CD-3) Water was added to make 1 liter, and the pH was adjusted to 10.10.

(Bleach-fixing solution) Ammonium ferric diethylenetriaminepentaacetate 100 g Diethylenetriaminepentaacetic acid 2 g Ammonium thiosulfate 120 g Ammonium sulfite 40 g Sulfinic acid 5 g Ammonium bromide 10 g Water was added to adjust the pH to 1 l, and the pH was adjusted to 7.0.

(Stabilizing solution) 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 Tinopal 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 the pH was adjusted to 8.0 using 50% sulfuric acid or 25% aqueous ammonia.

The processing tablets used in Example 2 were used.

Next, the above tablets were sealed one by one using a laminated polymer resin film made of PET / polyvinyl alcohol / ethylene copolymer / polyethylene, and charged using a supply device shown in FIG. The tablets color paper is turned one by one when it is 1 m ² processed simultaneously 76ml color developing tank replenishment water from replenishing water tank, bleaching fixing tank
It was set to supply 42 ml and 247 ml to the stabilization tank.

As a comparison, a running test was similarly carried out for water in which the water was supplied to the color developing tank, bleach-fixing tank, and stabilizing tank to the overflow port once every morning and evening.

As a result, the sensitivity variation in the case of the present invention was ± 1.
% Was within ± 4% when water was replenished to the overflow port every morning and evening, indicating that the photographic performance was stable when the evaporation and rehydration method of the present invention was used.

Example 5 A processed tablet for color paper was prepared according to the following procedure.

1) Replenishing tablet for color development for color paper Procedure (A) CD-3 [4-amino-3-methyl-N-ethyl-N- [β-
(Methanesulfonamido) ethyl] aniline sulfate] 1200
g is ground in a commercially available bandam mill until the average particle size is 10 μm. After granulating the fine powder in a commercially available stirring granulator at room temperature for about 7 minutes by adding 50 ml of water, the granulated material is dried at 40 ° C. for 2 hours in a fluidized bed drier. Almost completely removes water from the granules. Thus, 150 g of polyethylene glycol 6000 was added to the adjusted granules at 25 ° C and 40 ° C.
Mix evenly for 10 minutes using a mixer in a room humidified below% RH. Next, 4 g of sodium N-lauroylalanine
Was added and mixed for 3 minutes, and the obtained mixture was subjected to compression tableting with a tableting machine modified from Tough Press Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd. to make the filling amount per tablet 3.2 g, to obtain 400 tablets. Replenishing tablet A for color development for color paper
A preparation was made.

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 the granulation, the mixture is dried at 50 ° 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 granulated product,
Mix for 3 minutes using a mixer in a room conditioned at a temperature of 40 ° C. and below 40% RH. Next, the obtained mixture was mixed with a tableting machine obtained by modifying a tough press collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd.
Compression tableting was performed with the filling amount per tablet being 1.0 g to prepare 100 color developing and replenishing tablets B for color paper.

Operation (C) Tinopearl SFP (manufactured by Ciba Geigy) 30.0 g, sodium sulfite 3.7 g, potassium bromide 0.3 g, diethylenetriaminepentaacetic acid 25 g, sodium p-toluenesulfonate 280
g, 20 g of potassium hydroxide and 10.6 g of mannitol are pulverized in the same manner as in (A), and then uniformly mixed with a commercially available mixer. Next, in the same manner as in (A), granulation is performed with the amount of water added being 20 ml. After the granulation, the granules are dried at 60 ° C. for 30 minutes to almost completely remove the moisture of the granules. In this way, 4 g of N-lauroylalanine sodium was added to the prepared granules,
Using a mixer in a room conditioned at 5 ° C, 40% RH or less
Mix for a minute. Next, the obtained mixture was subjected to compression tableting with a tableting machine modified from Tough Press Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd., with the filling amount per tablet being 1.0 g, and 100 tablets.
A color developing and replenishing tablet C for color paper was 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 to be added is 20 ml, and after granulation, it is dried at 700 ° C. for 30 minutes to almost completely remove water from the granulated material. In this way, polyethylene glycol 6000 is added to the adjusted granules.
15 g is uniformly mixed for 10 minutes using a mixer in a room conditioned at 25 ° C. and 40% RH or less. Next, 4 g of sodium N-lauroylalanine was added and mixed for 3 minutes, and the resulting mixture was tough pre-collect 1527H manufactured by Kikusui Seisakusho Co., Ltd.
U was subjected to compression tableting using a modified tableting machine so that the filling amount shown in Table 1 was obtained, thereby preparing 110 color developing and replenishing tablets D for color paper.

2) Bleaching-fixing replenishing tablet for color paper Operation (E) Ethylenediaminetetraacetic acid ferric ammonium monohydrate 1250
g, 25 g of ethylenediaminetetraacetic acid, 250 g of maleic acid, and 46 g of pine flow (Matsuya Chemicals) in the same manner as in operation (C).
Mix and granulate. The addition amount of water is 80ml, and after granulation, 60 ℃
For 2 hours to remove the moisture of the granules almost completely.
15 g of N-lauroyl sarcosine sodium is added to the thus-prepared granules, and mixed for 3 minutes using a mixer in a room conditioned at 25 ° C. and 40% RH or less. Next, the obtained mixture was applied to Kikusui Seisakusho Co., Ltd. Tough Presto Collect 15
A tableting machine modified from 27HU reduces the filling amount per tablet to 8.
The tablet was compressed to 6 g and compressed and compressed to prepare 170 tablets A for bleach-fixing for color paper.

Procedure (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). Water spray amount is 10
After the granulation, the mixture is dried at 60 ° C. for 120 minutes to almost completely remove the water content of the granulated product. In this way, 20 g of sodium N-lauroyl sarcosine was added to the prepared granules,
Using a mixer in a room conditioned at 5 ° C, 40% RH or less
Mix for a minute. Next, the obtained mixture was subjected to compression tableting using a tableting machine modified from Tough Press Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd. so as to have the filling amount shown in Table 1, and a tablet B for bleaching and fixing for color paper was added. It was created.

3) Tablet for stable replenishment for color paper Operation (G) Sodium carbonate monohydrate 10 g, 1-hydroxyethane-1,1-
Disodium diphosphonate 200g, Tinopearl SFP150
g, sodium sulfite 300 g, zinc sulfate heptahydrate 20 g, ethylenediaminetetraacetic acid disodium 150 g, 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). The amount of water added
After granulation, the mixture is granulated and dried at 70 ° C. for 60 minutes to almost completely remove moisture from the granulated product. In this manner, 10 g of N-lauroyl sarcosine sodium was added to the prepared granules, and 2
Using a mixer in a room conditioned at 5 ° C, 40% RH or less
Mix for a minute. Next, the obtained mixture was subjected to compression tableting with a tableting machine modified from Tough Press Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd. so that the filling amount shown in Table 1 was obtained, and tablets for stable replenishment for color paper were prepared. .

Table 7 shows the refill tablets for color paper.
One tablet at a time shown in Table 8 and sealed four-sided with a laminated polymer resin film made of PET / polyvinyl alcohol / ethylene copolymer / polyethylene, and tableted for each replenisher part Then, the total amount was set to the amount shown in Table 2 so that the component ratio became the same as one tablet, and four-side sealing was performed in the same manner as described above. In addition, the packaging was made for 20 minutes per car.

Next, Konica Color QA Paper Type 5
(Manufactured by Konica Corporation) after imagewise exposure, the N shown in FIG.
It was processed by the modified PS-808 according to the following processing steps. However, the replenishing water in the replenishing tank used was one in which 0.1 g of benzisothiazoline was added per liter of the replenishing water.

Processing step Processing time Processing temperature Tank capacity Color development 22 seconds 38.0 ° C 12l Bleaching and 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 method from 3 to 1, and the entire overflow of Stable-1 was flowed into the bleach-fix tank. The 45ml carryover of the photosensitive material 1 m ² per light-sensitive material from the color developing tank to the bleach-fixing bath, 50m is to stabilizing tank from a bleach-fixing tank
1, 40 ml for stable-1 → 2,2 → 3 and 3 → dry.

The opening area of each of the color developing tank, bleach-fixing tank and stabilizing tank was 4.5 cm ² per liter of processing solution.

The following shows the composition of the processing solution.

(Color developing solution) Potassium bromide 0.02 g Potassium chloride 3.2 g Potassium carbonate 30 g Potassium sulfite 0.2 g Sodium diethylenetriaminepentaacetate 2 g Sodium nitrilotrimethylene phosphonate 2 g Tinopearl SFP 2 g Disodium-N, N-bis (sulfonateethyl Hydroxylamine 5 g 4-Amino-3-methyl-N-ethyl N- [β- (methanesulfonamido) ethyl] aniline sulfate 7 g (CD-3) Water was added to 1 liter to adjust the pH to 10.10.

(Bleaching and Fixing Solution) Ammonium ferric diethylenetriaminepentaacetate 100 g Diethylenetriaminepentaacetic acid 2 g Ammonium thiosulfate 120 g Ammonium sulfite 40 g Sulfinic acid 5 g Ammonium bromide 10 g Water was added to adjust to 1 liter, and the pH was adjusted to 7.0.

(Stabilizing solution) 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 Tinopal 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 the pH was adjusted to 8.0 using 50% sulfuric acid or 25% aqueous ammonia.

In the running experiment, the number of prints (E-version 3
750 sheets), and the tablet was evaluated for solubility, photographic performance, handleability, and the like.

Table 12 shows the tablet amount and the replenishing water amount.

[0363]

[Table 12]

The timing at which the tablets and the replenishing water enter are as follows: when the color paper is processed by 1 m ² , the color developing and replenishing tablets 7.85
g, replenishing water 80 ml, bleach-fixing replenisher tablets 39.7 g, replenishing water 200 ml, stable replenishing tablets 2.6 g, replenishing water 2
Replenish 50ml. Based on this amount, the addition time (Table 12) was changed according to the tablet amount. When the water replenishment amount reached the tablet amount, 80 ml, 200 ml, and 250 ml were supplied, respectively.

[0365]

[Table 13]

As a result, in terms of the workability of exchanging the tablet cartridge, the adhesion of the tablet to the packaging material, the solubility of the tablet, and the processing stability, all the replenishers are solidified and separated and replenished with replenishing water. In some cases, 0.5 g to 30 g was found to be 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 disodium ethylenediaminetetraacetate are crushed and granulated. The spray amount of water is 30 ml, and after granulation, it is dried at 60 ° C. for 60 minutes. Next, the granules are dried at 40 ° C. for 8 hours in a vacuum to remove the moisture of the granules almost completely.

The granules aged by the above operation were subjected to 25 ° C., 40% RH
Mix uniformly for 10 minutes using a mixer in a humidified room below. Next, the mixture was subjected to compression tableting using a tableting machine modified from Tough Press Collect 1527HU manufactured by Kikusui Seisakusho, with the filling amount per tablet set to 9.0 g, to prepare 200 color negative fixing replenishing tablets.

Next, 10 liters of a fixing solution having the following formulation was prepared.

[Composition of Fixing Solution] (1 L formulation) Ammonium thiosulfate 250 g Sodium sulfite 15 g Potassium carbonate 15 g EDTA-2Na 2 g Dissolution test unit (A) shown in FIG.
Filling the processing tank inside, made of Iwaki and magnet pump M
The tablets were placed in the auxiliary tank at a rate of one tablet per minute while circulating using D-5. Also, add 20 ml of water at the same time.
Each was added to the processing tank.

The temperature of the processing liquid in the processing tank and the auxiliary tank was changed by the temperature control unit as shown in the following table,
The remaining state of the tablets in the auxiliary tank at the time of injection was observed.

As a comparison, the same tablet and 20 ml of dissolving water were simultaneously added to the replenisher preparation unit every minute using the dissolution test unit (B) shown in FIG. 16 and stirred for 30 seconds with the stirring unit. Added to auxiliary tank. The liquid temperature of the dissolved water was 25 ° C.

[0374]

[Table 14]

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

As is clear from the above table, in the dissolving method of the present invention, in which the processing agent is directly charged into the processing solution, the temperature of the processing tank can be dissolved at 25 ° C. or higher without leaving any insoluble matter. , The dissolution speed can be controlled.

At 20 ° C., trace amounts of insolubles remained, but there was practically no problem.

Further, as in the unit (B) shown in FIG. 8, the method of dissolving with a replenisher preparation filter once does not dissolve within a specified time, so that all the components are clogged in the filter and cannot be operated.

In addition, assuming that the tablet was charged before the completion of the temperature control by the heater, charging was started 10 minutes before the completion of the temperature control, but there was no problem with dissolution in the unit (A). .

(Example 7) Konica Color Super DD-
After imagewise exposure of 100 films, the color negative film processor CL-KP-50QA was modified to a system that can use peel open packaging materials, and subjected to continuous processing.

[0381]

[Table 15]

Fixing is from 2 to 1, stability is 3 to 2,2
In this method, the bleaching tank was aerated with an air pump.

In addition, the evaporation correction is carried out at the time of temperature control in color development, bleaching, fixing-1, fixing-2, stable-1, stable-2, stable-.
10 ml, 6.5 ml, 7 ml, 7 ml, 8.6 ml, 1 hour each in 3 tanks
Evaporation correction was performed by a program that performs 8.6 ml and 9.3 ml of evaporative rehydration. When not operating, the non-operating time is accumulated, and color development, bleaching, fixing-1, fixing-2, stable-1, stable-2,
Evaporation-corrected water is stabilized at 7.5 ml / hour for 5 hours.
1, 6 ml, 6 ml, 5 ml, 5 ml, and 5 ml were collectively rehydrated at the start of operation. The tank liquid at the start was prepared using a replenisher of Konica Color Negative Film processing agent CNK-4-52 and a starter.

A processed tablet for color negative film was prepared according to the following procedure.

1) Tablet for replenishing color development for color negative Operation (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 vandam mill. And pulverize to an average particle size of 10 μm. This fine powder is granulated in a commercially available stirring granulator at room temperature for about 7 minutes by adding 10 ml of water, and the granulated product is dried at 40 ° C. for 2 hours in a fluidized bed drier. Almost completely removes water from the granules. In this way, 0.3 g of sodium N-lauroylalanine and 1.9 g of polyethylene glycol 6000 were added to the adjusted granules, and the mixture was mixed in a room conditioned at 25 ° C. and 40% RH or less using a mixer. Mix evenly for minutes. Next, the mixture was subjected to compression tableting with a tableting machine modified from Tough Press Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd. to make the filling amount per tablet 1.1 g, and 126 tablets A for color development and color development replenishment for color negative. It was created.

Operation (2) 69.4 g of hydroxylamine sulfate and 4 g of Pine Flow (manufactured by Matsutani Chemical) are ground in the same manner as in the operation (1), and then mixed and granulated. The amount of water to be added is 3.5 ml, and after granulation, the mixture is dried at 60 ° C. for 30 minutes to almost completely remove water from the granulated product. 0.3 g of N-lauroylalanine sodium is added to the thus-prepared granules, and mixed in a room conditioned at 25 ° C. and 40% RH or less using a mixer for 3 minutes. Further, compression tableting was carried out in the same manner as in the operation (1) using a tableting machine at a filling amount of 0.56 g per tablet to prepare 120 color negative color developing and replenishing tablets B for color negative.

Operation (3) Disodium 1-hydroxyethane-1,1-diphosphonate 15
g, 72.8 g of potassium sulfite, 375 g of potassium carbonate, 3 g of sodium bicarbonate, 3.7 g of sodium bromide and 22 g of mannitol are crushed and mixed in the same manner as in the operation (1), and granulation is performed with the added amount of water being 40 ml. . After the granulation, the granules are dried at 70 ° C. for 60 minutes to almost completely remove the moisture of the granules. 2 g of sodium N-lauroylalanine is added to the thus-prepared granules and mixed for 3 minutes using a mixer in a room conditioned at 25 ° C. and 40% RH or less. Further, compression tableting was carried out in the same manner as in the operation (1) using a tableting machine at a filling amount of 3.9 g per tablet to prepare 120 tablets C for color development and color replenishment for color negative.

2) Tablets for replenishing bleaching for color negatives Operation (4) Ferric ammonium ammonium monohydrate 1,3-propanediaminetetraacetate
175 g, 2 g of 1,3-propanediaminetetraacetic acid and 2 g of pine flow (manufactured by Matsutani Chemical Co., Ltd.) are ground and mixed in the same manner as in the operation (1), and granulation is performed with the addition amount of water being 8 ml. After the granulation, the granules are dried at 60 ° C. for 30 minutes to almost completely remove the moisture of the granules.

Operation (5) 133 g of succinic acid, 200 g of ammonium bromide and pine flow 1
Pulverize, mix and granulate 0.2 g as in operation (1). The amount of water to be added is 17 ml, and after granulation, it is dried at 70 ° C. for 60 minutes to almost completely remove water from the granulated material.

Operation (6) 66.7 g of potassium sulfate, 60 g of potassium hydrogen carbonate and 8 g of mannite are ground, mixed and granulated in the same manner as in the operation (1). The amount of water to be added is 13 ml, and after granulation, the mixture is dried at 60 ° C. for 60 minutes to almost completely remove water from the granulated material.

Operation (7) The granulated product prepared in the above operations (4) to (6) was treated at 25 ° C. and 40%
Mix evenly for 10 minutes using a mixer in a room humidified below RH. Next, 6 g of N-lauroyl sarcosine sodium is added to the mixed granules and mixed for 3 minutes. Next, the mixture was subjected to compression tableting using a tableting machine modified from Tough Press Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd., with the filling amount per tablet being 6.5 g, to prepare 80 color negative bleaching replenishing tablets. .

3) Fixing replenishment tablet for color negative Operation (8) 2500 g of ammonium thiosulfate, 150 g of sodium sulfite,
Operate 150g of potassium carbonate, 20g of ethylenediaminetetraacetic acid disodium salt and 65g of pine flow (Matsuya Chemical) (1)
Pulverize, mix and granulate in the same manner as described above. The amount of water to be added is 50 ml, and after granulation, the mixture is dried at 60 ° C. for 120 minutes to almost completely remove water from the granulated material.

Operation (9) The granulated product prepared in the above operation (8) and 13 g of N-lauroyl sarcosine sodium are mixed in a room conditioned at 25 ° C. and 40% RH or less for 3 minutes using a mixer. Next, the mixture was subjected to compression tableting with a tableting machine modified from Tough Press Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd., with the filling amount per tablet being 9.3 g, to prepare 280 color negative fixing replenishing tablets. .

4) Tablet for stable replenishment for color negative Operation (10) 150 g of m-hydroxybenzaldehyde, 20 g of sodium lauryl sulfate, 60 g of disodium ethylenediaminetetraacetate,
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). Water addition is 10
After granulation, the granulated product is dried at 50 ° C. for 2 hours to remove the moisture of the granulated product almost completely.

Operation (11) The granulated material prepared in the above-mentioned operation (10) was converted to a tough press collect 1527HU manufactured by Kikusui Seisakusho in a room conditioned at 25 ° C. and 40% RH or less using a tableting machine. Compression tableting was performed with the filling amount per tablet set to 0.48 g to prepare 280 color negative stable replenishing tablets.

Next, the tablets for color development and replenishment were prepared as follows: A, B, and C were used in two, one, and one tablets, respectively, for bleaching replenishment tablets, two tablets, for fixing replenishment tablets, three tablets.
As for the tablets for stable replenishment, each tablet was packaged in a 1-minute package, and each continuous 20-minute package was packaged in a four-sided sealing system using a peel-open packaging material. The same peel open packaging material as that used in Example 3 was used.

The timing of refilling tablets and makeup water was as shown in Table 16 above.

The processing was performed such that the overflow from the color developing tank tank was 5% of the tank liquid per day.

[0399]

[Table 16]

As a comparative example, the tablet and make-up water were used.
The solution was dissolved in the replenishing tank for 10 liters and replenished from the replenishing tank.
At this time, replenishment was performed so that the amount was the same as that of the tablet.

The evaporation correction was performed every morning up to the overflow port. Two months after the start of the processing, the photographic density of the highest density part was compared.

The results are shown in Table 17.

[0403]

[Table 17]

As is apparent from Table 17, up to such processing, in the conventional method of comparison, the color developing solution deteriorates and the photographic density is reduced. It turns out that it does not change at all.

Further, in the method of the present invention, the following liquid was used for one package in place of the tablet for stable replenishment, and similar results were obtained.

Diethylene glycol 2.9 g m-Hydroxybenzaldehyde 0.65 g Emulgen 810 (Kao Corp.) 0.2 g (Example 8) Next, regarding the relationship between the continuous state of treatment and the dissolution state of the solid processing agent, supply of replenishing water An example of control will be described.

[0407] The processing amount information is information that indirectly detects the situation where the processing agent component in the processing liquid decreases in accordance with the processing amount as described above. Therefore, when the processing is continuously performed and the processing agent component in the processing solution in the processing tank rapidly decreases, the supplement of the processing agent component due to dissolution of the processing agent to be replenished may not be enough. When the replenishing water is supplied only with the processing amount information, the replenishing water precedes the supplement of the above-mentioned processing agent components, so that the replenishing water temporarily becomes excessive and the liquid level of the processing tank is maintained by the overflow method. In the case of the method in which the treatment agent component is used, a phenomenon occurs in which the treatment agent component is diluted with the replenishing water, overflows and is discarded, and further decreases the treatment agent component, which is not preferable. In consideration of such a situation, in this embodiment, supply of the replenishing water is performed by a control unit that controls the operation in consideration of the dissolution time of the supplied processing agent or the dissolution and dispersion time of the supplied processing agent. By controlling, replenishment water is not supplied one after another while the treating agent is not dissolved or dissolved and dispersed.

FIG. 6 is a block diagram of the above embodiment.

The processing amount information is obtained by the detecting means 8,
The processing agent supply control means 9 and the replenishment water supply control means 9-b enter the processing agent supply control means 9 and the replenishment water supply control means 9-b. The replenishment water supply means 42 is controlled with reference to the data in Table 9-c. As described above, the supply of replenishing water when the treatment agent component of the treatment liquid in the treatment tank rapidly decreases due to the continuous treatment is performed after the dissolution or dissolution and dispersion of the treatment agent.

FIG. 17 shows a PTP (Pressure Through) according to the present invention.
Package) Regarding the device for charging the packaged solid processing agent,
(A) is a cross-sectional view of the processing agent supply device, (B) is a perspective view of the packaging breaking means, (C) is a perspective view of the packaging breaking means, and (D) is
Sectional drawing which shows the loading state of the solid processing agent packaged by PTP.

[0411] The processing agent storage container stores the solid processing agent packaged in PTP, and may be individually stored in the storage container or may be a cartridge type in which the solid processing agent is stored in advance. A known material can be used for the PTP packaging, and the solid processing agent is preferably packaged in a tablet form.

[0412] The solid processing agent packaged in PTP is supplied from below the storage container. When a predetermined amount of the photosensitive material is processed, the information of the processing amount detecting means is sent to the processing agent supply control means, and the PTP-packed solid processing material is sent by the motor. The lower part of the PTP package (mainly made of aluminum) is peeled off by extruding the processing agent into a wedge-shaped fixing plate and crushing it, and the solid processing agent is injected into the processing tank from the inlet. After emptying, the empty PTP package is further pushed out and discarded from the disposal port. As a means for crushing, there is a method using a roller other than using a wedge, and any method can be used.

FIG. 18 shows an example of a parts feeder type feeding device for tablets (previously divided and weighed) packaged together according to the present invention.

[0414] Packaging material A or B for tablet chemicals packaged together
Was opened and put into the hopper 101. At that time, no fine powder was generated, and there was no caking and the handleability was good.
The stirrer 106 is rotated by the signal of the remaining amount detection means 109,
Are aligned with the tablet aligning unit 110. The processing agent supply control means 103 operates according to the processing amount of the photosensitive material, and the turntable 107 conveys the tablets and supplies the tablets from the discharge unit 108 to the input unit. The turntable 107 makes one turn, and the turntable 107 makes one turn, and stops at an instruction from the turntable control means (tablets can be supplied several times with one instruction). The tablet enters the hole of the turntable 107.

[0415] Packaging materials are inexpensive and easy to handle.
There is an advantage that the feeding can be performed with high accuracy, and especially since the tablet aligning section 110 is provided, there is no empty supply from the rotary table and the efficiency is very high. Environmentally friendly due to reduced plastic containers. In addition, since there is no fine powder, the inside of the supply device is free of contamination and maintenance-free.

Another embodiment of the present invention is shown in FIG.
Except that the drying air 962A generated from 0 is directly sent to the processing agent supply means 101 through the duct 962, the tablet 13 can be dried more efficiently. Is the same.

Thus, the storage of the tablet 13 is stable and long-term storage is possible.

FIG. 19 shows an example of a parts feeder type feeding device 120 for tablets (previously divided and weighed) packaged together according to the present invention.

The package material (A) or (B) of the packaged tablet chemical was opened and placed in the hopper 133. At that time, no fine powder was generated, and there was no caking and the handleability was good. The movable member 124 is rotated by a signal from the remaining amount detection means 125, and the tablet chemicals are aligned in the tablet alignment section 129. After a certain amount of alignment, the movable member 124 stops. At this time, Sweeper 123
However, it is very effective for the tablet to enter the pocket 122 of the movable part 124 and to be aligned with the alignment part 125.

Means for supplying a processing agent in accordance with the processing amount of the photosensitive material
126 works, the first shutter 131 rotates, and the tablet chemical falls down. Next, the first shutter 131 is rotated in the reverse direction to clamp one tablet between the shutters 131 and 132. Shutter 132
Rotates, and the tablet chemical passes through the discharge unit 128 and is supplied to the input unit. Next, the shutter 132 rotates in the reverse direction, and the shutter 131 closes.

The packaging material is inexpensive, has good handleability, and can be charged with a high degree of accuracy. In particular, since the tablet aligning unit 129 is provided, there is no empty supply, so that it is good. Environmentally friendly due to reduced plastic containers.
Further, since the fine powder is not present, the inside of the supply device is not stained and is maintenance-free.

Another embodiment of the present invention is shown in FIG.
19 except that the drying air 962A generated from 0 is directly sent to the processing agent supply means 133 through the duct 962 so that the tablet 13 can be dried more efficiently. Is the same.

Thus, the storage of the tablet 13 is stable and long-term storage is possible.

FIG. 22 is a perspective view showing an example of the solid processing agent supply device 140 of the present invention, in which the solid processing agent is put into a processing tank by removing the package of the solid processing agent contained in the package. It is.

[0425] The leading end of the storage packaging material in which the solid processing agent is packaged in a four-sided seal is set on a winding shaft 142 as a fixing means via a roller 141, and when the photosensitive material is processed, it is detected by the processing amount information detecting means. Then, when a certain amount is reached, a signal is sent by the processing agent supply control means, and the motor of the winding shaft 142 which is also the processing agent supply means is operated, so that the package body containing the solid processing agent is fixed to a certain length. Just move
Add the required number of solid processing agents. The method of moving the package may be any method such as a method of detecting a notch provided in the package in advance, a detection of a printed pattern, and a detection of a processing agent of the package. , Roller 14
It is moved by 1 or the take-up shaft 142. The roller 141 is provided for the purpose of fixing or positioning the package, is separated by two winding shafts, and the solid processing agent is supplied.

In the case of such a system, the solid processing agent is granules,
Pills, tablets, and powders may be used, but preferably tablets have the advantage that they do not adhere much to the seal, and thus can be charged with high accuracy and that dirt is less likely to occur. After the winding is completed, the cartridge may be taken directly from the winding shaft, or may be rewound and the package may be discarded together with the cartridge.

FIG. 23 shows an example of a supply device according to a preferred embodiment of the present invention, wherein (A) is a plan view, (B) is a perspective view,
(C) is a plan view of various packages.

The treatment agent 151 is packaged in a package 152 sealed on all sides in a form as shown in FIG.

The packaging form shown in FIG. 23 (C) is an example of the present invention, and the present invention can be achieved by the effect of the dehumidifier 960 even if the material used for the packaging is paper having low moisture resistance.
A commonly used polymer resin package, aluminum, or a composite material is used. In other words, the object of the present invention can be achieved by using a material having good moisture resistance and low oxygen permeability.

[0430] The processing agent 151 sealed in all directions is peeled off via the cylinder 153, and the processing agent 151 is supplied through the input port 154 into the input section 155.
It is thrown into. Here, the cylinder 153 and the winding shaft 156 function as a processing agent supply unit. The package 152 has a winding shaft 156.
The winding is controlled by a processing agent supply unit that receives a signal from the photosensitive material processing amount detection unit. When winding, the knob is opened, the tip of the package 151 is set on a winding shaft 156 which is a fixing means of the processing agent storage packaging material via a cylinder, and the knob 157 is fixed by the clamper 158 by twisting the knob. Rolled up.

FIG. 24 shows an example of the supply device 160 when the solid processing agent 161 is packaged in a stick.
(A) is a side sectional view, and (B) is a front sectional view.

The stick-wrapped solid processing agent 161 is placed in a storage container 162 as storage means. The solid packaging agent 161 in the stick container 162 contained in the container 162
Then, it is sent to the turret 164 by a roller that also serves as a supply to the turret. The stick packaging solid processing agent 161 sent to the turret 164 is fixed at both ends by the clamper 165, and then sent to the cutter unit by a rotating motion, where the center of the stick packaging is cut (or cut) by the cutter 166 and further rotated. Then, the solid processing agent 161 filled in the stick package is fed into the chute 168 from the portion cut by the rotary cutter 166. After throwing in, scrap rotation bar 169
To the clamper 165 by the clamp opening / closing cam 170.
Is released. The scrap 171 in the scrap packaging is discarded in the collection chute 172.

FIG. 25 is a sectional view showing an embodiment of the present invention.

The processing section 181 and the charging section 185 in the constant temperature bath 182 which constitutes a part of the processing tank are in communication with each other.
It is discharged to 82 and enters the processing section 181 through the tablet input section 185.

When the photosensitive material is processed, the processing amount detecting means 19
The processing amount is detected by 2, and when a certain processing amount is reached, the motor M2 is driven via the processing amount supply control, and the pre-weighed tablets are supplied to the charging section 185 in the thermostat 182. I have.

The tablets are directly loaded into the storage container 187, and after being loaded, the aligning means 188 is driven by the motor M1 according to a signal from the alignment amount control means 186 to align the tablets, and is supplied to the aligning section 189. The tablets supplied to the aligning unit 189 receive a signal from the processing amount supply control unit 190, and when the motor M2 is driven, the tablets are carried to the upper part of the input unit by the rotational movement of the supply unit and are input to the input unit 185. At that time, processing agent supply means 191
In a preferred embodiment, it is substantially shielded from the thermostat 182 from the viewpoint of the moisture resistance of the tablet.

[0437] The tablets to be put into the storage container 187 are shown in FIG.
(A) and (B) are broken and put into a charging container 187. The containers shown in FIGS. 25 (A) and 25 (B) can be made of known materials such as paper and high molecular weight resin aluminum, but are preferably made of materials having good moisture proof properties and low oxygen permeability. .

FIG. 26 is a sectional view showing an example of a supply device 200 for a solid processing agent packaged in blisters.

The individual packaging 202 containing the solid processing agent is placed in the storage section 203.
To load.

The disk 201 is rotated by 180 ° according to the processing amount of the photosensitive material.
After rotating, the needle 205 penetrates the individual package 202, passes through the discharge unit 204 in the individual package 202, and supplies the input unit. Empty individual packaging 202
Is discarded from the disposal port.

The solid processing agent may be a powder or a granule, but a granule is preferable since the powder adheres to the container.

The handling property is good, and the supply device 200 is free of fine powder contamination and maintenance-free.

FIG. 27 is a sectional view showing an example of the present invention.

In accordance with the processing amount of the photosensitive material, the material is directly supplied from the tablet chemical storage section 211 to the input section 215 in the processing tank. The input unit 215 has a solid processing agent filter 216 so that the undissolved processing agent does not directly adhere to the photosensitive material. The material of the filter 216 is not particularly limited. The mesh is not particularly limited, but is preferably 10 to 100 μm from the viewpoint of the flow of the liquid and the filter effect.

The effect is almost the same as when the solid processing agent is supplied to the constant temperature bath 212 which forms a part of the processing bath. Only one additional charging section 215 in the processing tank is inferior in compactness.

[0446] Next, specific examples of packaging of the four-sided seal and the three-sided seal are shown in Figs. However, the present invention is not limited to these. In the seal package shown in FIG. 28A, several kinds of tablets are contained in one package unit. In FIG. 28B, tablets of different types and sizes are individually mounted. FIG. 28 (C)
Is a package of granules or powder. FIG. 28 (D) includes ones having the same size one by one. In FIG. 28 (E), a plurality of the same chemicals having the same size are contained as small tablets.

FIGS. 25 (F), (G) and FIG. 29 (H)
This is an example in which powder or granules are packaged and the constituent units to be charged at one time are changed.

FIGS. 29 (I), (J) and (K) show an example in which different kinds of tablets are put in the same package, and their constitutional units are changed.

FIGS. 29 (L), (M), (N) and (O) show the case where the number to be put in the same package is changed.

[0450] Fig. 29 (P) shows a continuous package containing powder or granules separated.

FIGS. 29 (Q) to (X) show examples in which the tablets containing tablets are separated.

FIGS. 30A, 30B and 30C are plan views showing examples of four-sided seals. FIG. 30D shows an example of a three-way seal. FIGS. 31A and 31B show specific examples of stick packaging, but are not limited to these.

FIG. 32 is a cross-sectional view showing a state in which tablets, granules, or powders are sealed and sealed, heat-sealed, folded, and stored in a container.

FIG. 33 shows a specific example of PTP packaging. However, it is not limited to these. FIG. 33 (A) shows a pill-like solid processing agent packaged in PTP, and FIG. 33 (B) shows a state in which a plurality of tablets of the processing agent are packaged.
FIG. 33 (C) shows a state in which tablets, granules or powders are arranged in tandem. FIG. 33 (D) shows these packages connected in one horizontal row. Alternatively, it may be a blister as shown in FIG.

[0455] Fig. 34 shows a specific example of batch packaging. However, it is not limited to these. FIG. 34 (A) shows a case where a solid processing agent is stored in a cylindrical container, FIG. 34 (B) shows a case where a solid processing agent is stored in a flexible two-sided or three-sided sealed bag,
FIG. 34 (C) shows a bag in which the solid processing agent is accommodated, one side of which is sealed.

FIGS. 35 and 36 are perspective views showing specific examples of the cartridge.

These cartridges can be mounted on the supply device of the automatic processing machine of the present invention as they are as the packaging material containing the solid processing agent. As the material, any of the compounds described above can be used. When the amount of the solid processing agent decreases, it is preferable that the solid processing agent does not collapse so as not to hinder the supply.

[0458] Fig. 35A shows a case where tablets are stored in a cylindrical cartridge, and Fig. 35B shows a case where granules or powders are stored in a cartridge.

FIGS. 35 (C) and (D) are a perspective view and a sectional view showing a form in which a solid processing agent is accommodated in a box-shaped cartridge having an opening / closing lid.

In FIG. 36, tablets, granules, or powders are stored in a rotatable container having partition walls, further stored in an outer cylinder (main body), and dropped by a predetermined amount from an opening. FIG. 36 (A) shows a type in which the rotating shaft is horizontally supported,
FIG. 36B shows a type in which the rotating shaft is vertically supported.
Note that the present invention is not limited to these specific examples.

Further, FIGS. 37 (a) and (b) and FIGS. 38 (a) and (b)
Another embodiment of FIGS. 39, 40 and 41 will be described.

FIGS. 37 (a) and 37 (b) are cross-sectional views of a "U-shaped" half punching apparatus.

When the photosensitive material is processed, it is detected by the processing amount information detecting means. When the processing amount information reaches a certain amount, a signal is sent by the processing agent supply control means, and the transport roller 100 rotates, and the solid processing agent 13 The package 801 shown in FIG.
Is moved to a position as shown in FIG. Package
The method of moving the 801 may be any method such as a method of detecting a notch provided in the package 801 in advance, a detection of a printed pattern or an eye mark, and a detection of the treatment agent 10 of the package 801. What is necessary is just to detect the agent 13 accurately. Next figure
As shown in FIG. 37 (b), the punch male mold 300 moves downward to cut the package 801 and the solid processing agent 13 passes through the input port 901 in FIG. 38 (a).
It is put into the processing tank of the automatic processor. The cut cut by the punch male mold 300 has a punch shape 60 as shown in FIG.
It becomes U-shaped like 1.

In the case of such a system, the solid processing agent 13 may be any of powders, granules, and tablets, but is preferably a male punch and a tablet to which a chemical is unlikely to adhere. Further, the tablets 13 do not adhere to the package so much that they are not easily stained, and are safe for the user to handle. Used packaging body 802 is waste box 6
02 can be put together and discarded. This waste box 60
2, it is preferable to reuse the used package storage box 701.

FIGS. 39 and 40 show a method of cutting off the package 801. FIGS.

When the photosensitive material is processed, it is detected by the processing amount information detecting means. When the processing amount reaches a certain amount, a signal is sent by the processing agent supply control means, and the transport roller 201 rotates, and the solid processing agent 13 The solid processing agent 13 moves the packed package 801 to a position above the processing tank filter unit 902 and stops. At this time, the tip of the package 801 is in the ironing roller 401.

The method of moving the package may be any method such as a method of detecting a notch provided in the package 801 in advance, a detection of a printed pattern, and a detection of processing of the package. What is necessary is just to detect accurately. Next, the ceramic cutter 201 cuts the package 801. When the cutting is completed, the ironing roller 401 and the transport roller 501 rotate to rotate the solid processing agent 13.
It is squeezed by the squeezing roller 401, passes through the discharge port, and enters the processing tank filter unit 902 of the automatic developing machine. The cut waste package 802 is discharged from the transport roller 501 and enters the waste box 602. It is preferable to reuse the used package storage box for the waste box 602.

In the case of such a method, the solid processing agent 13 may be any of powder, granules and tablets, but preferably a tablet to which the chemical does not adhere to the ceramic cutter 201. Further, there is an advantage that the tablet does not adhere to the package body 802 to a large extent, so that stains are hardly generated.

[0469] The used packages 11 can be put together in the disposal box 602 and discarded.

FIG. 41 (a) and FIG. 41 (b) show a two-part cutting method for the continuous package 603.

When the photosensitive material is processed, it is detected by the processing amount information detecting means. When the processing amount information reaches a certain amount, a signal is sent by the processing agent supplying means and the transport roller 502 is rotated, and at the same time, a ceramic or stainless steel round is formed. The blade 301 rotates and cuts the lower part of the continuous package body 603 into two parts to remove the solid processing agent 1
Input 3 The repackaged body 603 divided into two parts is spread on both sides by suction at the suction guide 202, so that the solid processing agent 13 inside is easily dropped. The empty package 603 without the solid processing agent 13 moves by the transport roller 401 when the next solid processing agent 13 is charged, and is discarded in the package storage box 101.

[0472] In addition to the above-mentioned method, a notch or the like may be attached to the continuous package, and the two parts may be torn while being wound by a roller.

In the case of such a system, the solid processing agent 13 may be any of powder, granules and tablets, but is preferably a tablet to which the chemical does not adhere to the male punch. Further, the tablet does not adhere to the seal of the package so much that there is an advantage that dirt hardly occurs.

The used package 603 can be put into the package storage box 101 and discarded as a whole.

[0475]

As described above, the automatic developing machine for silver halide photographic light-sensitive material of the present invention directly adds a solid processing agent divided and weighed in advance to a processing tank and dissolves it. The photographic performance is kept constant by replenishing the components or dissolving the components, and replenishing the necessary amount of replenishing water as needed.

[0476] Conventionally, it is unnecessary for the user to prepare a replenisher for each fixed period, and the processing solution can be automatically added in accordance with the processing amount of the photographic material simply by setting the solid processing agent in advance in a set. Performance is kept constant.

Further, by constituting the water-in-gas separation device so as to separate the water by sucking the gas outside the automatic developing machine, the air in the vicinity of the automatic developing machine is dehumidified. The deterioration of the solid processing agent stored in the supply means due to humidity can be suppressed.

Further, by introducing the dry air generated by the gas / water separator into the solid processing agent supply means, the effect of suppressing the deterioration of the solid processing agent accommodated in the solid processing agent supply device due to humidity can be further enhanced. can do.

Further, since the water separated by the water-in-gas separation device can be used as it is in the replenishing water replenishing device of the automatic developing machine for solid processing agents, the size of the automatic developing machine can be reduced. Labor saving of water supply work required for treatment is possible.

In addition, the replenishment tank volume is 4 to 4 for color negatives.
Since five types of liquids are required, 40 to 50 liters are not required, and the size can be reduced. Also, the replenisher in the conventional replenisher tank has a floating pig and the storage stability for about two weeks was not guaranteed, but in the age of low replenishment, the replenisher of 10 l has been used for more than one month, and its storage stability has been improved. What was a low and serious problem could be solved at once.

In the replenishment solution of the low replenishment era, the concentration was achieved by using the performance up to the solubility limit of the chemical, and the concentration of each replenishment solution was 1.4 to 2 times that of the used solution. Therefore, during storage in the winter, there were problems such as precipitation of crystals and generation of tar, which caused damage to photographic materials to be processed. It can be seen that such a problem is completely solved by the present invention.

That is, in the present invention, only a liquid having a low concentration, such as a processing liquid used, exists. This is because the solid processing agent is used to make up for the shortage, so that the solid processing agent does not basically have a higher concentration than the processing solution used.

For the above reasons, the conventional replenishment method could not be reduced in replenishment because the replenisher could not be concentrated any more due to the solubility limit. In particular, the color developing replenisher for color paper and the bleach-fixer, which could not be replenished because the stability was too low, could be replenished by the solid processing agent replenishing method of the present invention. become. Further, all of them are achieved and realized by the replenishment method of the present invention in which no replenisher is present.

The solid processing agent has less risk of transportation and does not require the container to be robust. There are no transportation safety regulations such as liquid dangerous goods, and packaging can be simplified. It has high safety in transportation and handling in shops, and has the advantage of not damaging or soiling human bodies and clothes.

However, solid processing kits were disadvantageous in that they were difficult to dissolve, and solid kits were generally used in the past. However, recently, dissolution work takes a long time, so most of them are liquid type and supplied as liquid. It was like. The present inventors have conducted intensive studies on this point, and as a result, there is no problem even if the solid processing agent divided and weighed in a small amount is dissolved over time by directly charging the solid processing agent into a processing liquid tank temperature-controlled at a constant temperature. It has been discovered that replenishment work can be performed to maintain stable photographic performance.In other words, it is necessary to store the replenisher once completely dissolved in the replenisher tank and inject it into the processing tank as needed to maintain the components. The replenisher kit which has been considered to be required to be used at least in a processing tank in which a solid processing agent divided and weighed in advance according to the processing amount information of the silver halide photographic light-sensitive material according to the present invention is adjusted to a constant temperature. 1
The replenishment tank is periodically charged and replenished water is supplied periodically to a part of the same processing tank as needed, eliminating the need for complicated dissolution of the chemical replenisher by the user. Elimination of dangerous and dangerous concentrated liquid chemical kits and conventional chemical bottles containing them has been achieved, and since there is no replenishment tank, there is no replenisher and the lifetime of the solution has been significantly improved. Since the solid processing agent can be stably stored for a long period of time, the processing stability can be dramatically improved.

Also, there is a method called AR replenishment, in which the replenisher is dissolved in advance before use, and replenishes ABC3 sachets of the concentrated liquid kit and replenishment water by directly dispensing with a bellows metering pump. Although it has been implemented, considerations have been made such as adding the four components in advance rather than directly putting them into the processing tank separately, and this has not been done with a solid processing agent. .

[Brief description of the drawings]

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

FIG. 2 is a sectional view of a processing agent supply section and a processing agent supply unit of the automatic developing machine.

FIG. 3 is a cross-sectional view of a processing agent supply unit and a processing agent supply unit of the automatic developing machine to which a replenishing water supply unit is added.

FIG. 4 is a plan view of the automatic developing machine.

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

FIG. 6 is a block diagram in which a melting table is added to control means of the automatic developing machine.

FIG. 7 adds a means for introducing dry air to the processing agent supply means. FIG. 2 is a plan view of the automatic developing machine.

FIG. 8 is a sectional view of a processing agent supply unit of the automatic developing machine.

FIG. 9 is a plan view of an automatic developing machine to which means for sucking air from a drying unit is added.

FIG. 10 is a plan view of an automatic developing machine to which a means for performing suction from the upper portion of the processing tank is added.

FIG. 11 is a plan view of an automatic developing machine to which a means for circulating a gas between a solid processing agent supply means and a water-in-gas separation device is added.

FIG. 12 is a schematic sectional view of a dehumidifier using a Peltier element.

FIG. 13 is a perspective view showing a schematic configuration of a dehumidifier using a semipermeable membrane for separating water.

FIG. 14 is a characteristic diagram of a replenishing amount and a concentration ratio.

FIG. 15 is a configuration diagram of a dissolution test unit.

FIG. 16 is a configuration diagram of a dissolution test unit.

FIG. 17 is a cross-sectional view and a perspective view of a PTP packaging treatment agent supply device according to the present invention.

FIG. 18 is a sectional view showing another embodiment of the supply device.

FIG. 19 is a sectional view showing still another embodiment of the supply device.

FIG. 20 is a sectional view showing still another embodiment of the supply device.

FIG. 21 is a sectional view showing still another embodiment of the supply device.

FIG. 22 is a perspective view showing still another embodiment of the supply device.

FIG. 23 is a plan view and a perspective view of a supply device, and a plan view of a package.

FIG. 24 is a side sectional view and a front sectional view of the supply device.

FIG. 25 is a sectional view of a supply device and a perspective view of a package.

FIG. 26 is a cross-sectional view of a supply device for a solid processing agent packaged in individual blisters.

FIG. 27 is a sectional view showing an example in which a solid processing agent is directly added to a processing tank.

FIG. 28 is a plan view of a seal package.

FIG. 29 is a plan view showing various embodiments of the seal package.

FIG. 30 is a plan view showing a specific example of three-sided and four-sided seal packaging.

FIG. 31 is a plan view showing a specific example of stick packaging.

FIG. 32 is a sectional view showing another specific example of the stick packaging.

FIG. 33 is an explanatory view showing a specific example of PTP packaging.

FIG. 34 is a perspective view showing a specific example of batch packaging.

FIG. 35 is a perspective view and a sectional view showing a specific example of a cartridge.

FIG. 36 is a perspective view showing another specific example of the cartridge.

FIG. 37 is a cross-sectional view of an apparatus for cutting a package by half-cutting it into a U-shape.

38 is a perspective view and a plan view of an apparatus for half-cutting the package shown in FIG. 37 in a U-shape.

FIG. 39 is a sectional view of an apparatus showing a method of cutting off a package.

FIG. 40 is a perspective view of an apparatus showing the cutting-off method of FIG. 33;

FIG. 41 is a perspective view and a cross-sectional view of an apparatus showing a two-part cutting system for a continuous package.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Processing tank 1A-1E Processing tank 1R Rack 2 Processing part 3 Filter 4 Circulation pipe 5 Circulation pump 6 Drainage pipe 7 Heater 8 Processing amount information detection means 9 Processing agent supply control means 10 Extrusion member 11 Solid processing agent input section 12 Partition Wall 13 Solid photographic processing agent, (tablet) 14 Filtration unit (section) 14A Stirring blade 14B Stirring blade 14C Shear gear 14D Vibrator 14E Magnetic rotating blade 14F Rotating magnet 14L Transmission mechanism 14M Motor 14N Partition member 14P Injection pump 15 Cartridge 16 Lead wire 17 Treatment agent supply means 17a Solid treatment agent supply means 17a Treatment agent supply means with an additional intake port and exhaust port. 18 Push claw 19 Cam 21 Tablet press spring 23 Pre-programmed evaporative rehydration setting means 24 Tablet stopper 25 Screw 27 Screw 28 Container 29 Treatment agent guide 32 Hot water replenishment device 33 Solenoid valve 35 Drying unit 36 Refill pipe 41 Pipe ( (For refilling) 42 Replenishing water supply means 43 Refilling tank

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁷ , DB name) G03D 3/06 G03C 5/26 G03C 7/00

Claims (6)

(57) [Claims] 1. A a process vessel for containing a processing solution for processing an exposed silver halide photographic light-sensitive material, a housing means to accommodate the pre-divided weighed solid processing agent is the divided weighed into the processing tank Supply means for directly charging the solid processing agent, processing amount detecting means for detecting processing information of the silver halide photographic light-sensitive material, processing amount information of the silver halide photographic light-sensitive material detected by the detecting means Control means for controlling the supply means in response to the supply of the solid processing agent, and a water-in- gas separation device for separating moisture in the gas and discharging dry air , wherein the separation in the gas-in-gas separation device is performed. The treated water into the treatment tank
Having a replenishing device for supplying and reusing the water , and drying simultaneously generated by the water-in-gas separation device.
Introducing air into the supply means and / or the storage means
Automatic developing machine for silver halide photographic light-sensitive material characterized by comprising means that. 2. The automatic silver halide photographic light-sensitive material according to claim 1, wherein said solid processing agent is a powdery, granular, or tablet-formed tablet which has been divided and weighed in advance. Developing machine. 3. The automatic developing apparatus for a silver halide photographic light-sensitive material according to claim 1, wherein said water-in-gas separating apparatus sucks a gas outside the automatic developing machine. Machine. 4. The halogenation apparatus according to claim 1, wherein the apparatus for separating moisture in a gas is configured to take in gas in a drying section of an automatic developing machine. Automatic developing machine for silver photographic photosensitive materials. 5. The apparatus according to claim 1, wherein the apparatus for separating moisture in a gas sucks a gas in an upper portion of a processing tank of an automatic developing machine. Automatic developing machine for silver halide photographic materials. 6. The apparatus for separating moisture in a gas as described below.
(A) at least one device selected from (c)
Is constituted by a method (1).
The silver halide photograph according to any one of (1) to (5).
Automatic developing machine for photosensitive materials . (A) a device for condensing gas by a heat pump or
Method (b) Apparatus for condensing gas with an electronic cooling element or
Method (c) A semipermeable membrane that separates water vapor from gas
Separation device or method