JPH07110550A - Solid color developing agent for silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To complete a completely automatic replenishing system with no need for a user to manually dissolve a concentration kit and to supply the solid color developing agent for a silver halide photographic sensitive material with the processing stability drastically improved. CONSTITUTION:This solid color developing agent 13 for a silver halide photographic sensitive material contains a p-phenylenediamine compd. having at least one kind of water-soluble group and a carbonate and is directly charged into a processing tank 1 of an automatic developing machine by a unit supply at a time. When the number of mols of the compd. in the agent 13 is denoted by (y) and that of the carbonate by (x), 0.092<=y/x<=0.5, and the unit supply of the agent 13 is controlled to 0.5-50g.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a processing agent for silver halide photographic light-sensitive materials. More specifically, it is a chemical waste liquid which can be improved in workability by making an automatic developing machine compact and eliminating melting work. The present invention relates to a color-developing solid processing agent for silver halide photographic light-sensitive materials, which leads to a reduction in the amount and the chemical stability is dramatically improved.

[0002]

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

A liquid having a processing function for performing each of these processing steps is called a processing liquid. Each treatment liquid is usually 30 ~
The temperature is adjusted to 40 ° C., and the light-sensitive material is dipped in these processing solutions and processed.

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

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

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

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

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

In this case, the replenishing liquid itself stored in the replenishing tank is generally prepared and prepared in another place, but in a minilab or the like, the replenishing tank is installed in a constant amount in a replenishing tank installed close to the developing machine. It is usually adjusted all at once, but in its production, dissolution by hand or dissolution and mixing by a mixer has been performed.

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

[0011]

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

Replenishing processing agents are divided into several parts in order to obtain good and stable performance during photographic processing. The color developing solution for color is divided into 3 to 4 parts, and the replenisher for the bleach-fixing solution for color is divided into a ferric salt of organic acid which is an oxidizing agent and a thiosulfuric acid part which is a reducing agent. When the replenisher is prepared, the concentrated part of the ferric salt of organic acid and the concentrated part containing thiosulfate are mixed and a certain amount of water is added for use.

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

The replenishing treatment agent in which the above-mentioned part agent is made into a kit is used after dissolving, diluting, mixing and finishing to a fixed amount, but the replenishing treatment agent has the following drawbacks.

First, most of the conventional kits are concentrated and concentrated aqueous solutions for improving workability, and most of them are extremely dangerous aqueous solutions with a pH of 2.0 or less or 12.0 or more. Many of them are very dangerous and are often strong oxidizers or reducing agents, and they have extremely dangerous corrosiveness when transported by ship or aircraft. Further, since it is an aqueous solution, its solubility is limited, and its weight and volume are larger than those of a solid. As mentioned above, since the concentrate is a dangerous substance, it is necessary that the container does not break even if dropped from a certain height and the liquid does not spill. Is a problem.

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

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

Fourth, the chemical is very unstable.

The life of the replenisher is usually 2 weeks even with the floating lid. However, recently, the replenishment amount of each processing solution has been lowered, and 10 L of the replenishing solution is often used for more than one month in a minilab that receives an average of 30 color films per day.

In such a case, the replenishing solution in the replenishing tank is much more exposed to air than the treating solution in the processing tank and is deteriorated. is happening. Therefore, 5L refill tank
The device is designed to be small and the storage unit of the replenishment kit is set to 5 L. In this case, there is a drawback that a packaging material is further required.

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

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

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

Another problem is that the replenisher is only thickened while the replenisher is being made lower and faster, and the recent replenisher is usually concentrated to the solubility limit.

[0025] This means that the retentive solution is not only storable but also has many practical problems such as crystal precipitation.

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

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

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

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

Several methods have been proposed to eliminate the plastic container and improve the chemical stability of the replenisher by methods other than the above.

For example, Japanese Patent Application Laid-Open No. 58-11032 discloses a technique of encapsulating a developing component in microcapsules, and Japanese Patent Application Laid-Open No. 51-51.
-61837 discloses a photographic tablet containing a disintegrant. Furthermore, JP-A Nos. 2-109042 and 2-109043,
3-39735 and 3-39739 disclose a method of using a granulated photographic processing agent having a certain average particle diameter.

The photographic tablet containing the disintegrant described in JP-A No. 51-61837 is merely a tablet that can be easily dissolved in water, and the solid processing agent is directly added to the processing tank of the present invention. The idea of dissolution cannot be recalled at all.

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

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

On the other hand, as a method for eliminating the need for a prior dissolution operation, Japanese Patent Laid-Open No. 3-11344 discloses extruding a paste-like part agent from each unit container in an amount corresponding to the mixing ratio of the part agent, and extruding the part agent. Although a technology for accurately adjusting and supplying the part agent by diluting it to a predetermined concentration is disclosed, this method surely reduces the dissolution work or almost eliminates the dissolution work, but it is a paste form. Since the part agent contains a solvent, it lacks stability, and it is difficult to extrude a certain amount for a long period of time. If the part agent is not used frequently, the nozzle is likely to be clogged, and it is difficult to keep the photographic performance constant. Further, a container for containing the paste is required, and in this case, a flexible and hard-to-break material is required, and a composite material that is generally difficult to reuse is used, which is not environmentally friendly. In particular, it is known that pasty chemicals are often formed into a paste by an organic solvent and have poor storage stability.

Further, Japanese Utility Model Laid-Open No. 1-85732 discloses an automatic processor having 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 feeding, and this does not remind the treating agent replenishment control means.
This is not mandatory because the purpose is to preserve the liquid itself.

WO 91-07698 and WO 91-07699 disclose a method in which CD-3 or CD-4 is added as a solid and other components are added as an activator in a liquid form. Is related to regeneration, and is an invention relating to low replenishment, which is as close as possible to no overflow, and after removing bromide ions and chloride ions from the developer by an ion exchange resin, the alkali agent activator and solid or small amount of the insufficient component are removed. It is a method for adding a concentrated color developing agent and adding components without increasing the volume.

Further, in Japanese Patent Application Laid-Open No. 4-237045, the powdery treatment agent is set for each part in an automatic developing machine and directly weighed in the required amount into the treatment tank. A technique that may be added is disclosed.

Certainly, this technique eliminates the conventional work of dissolving the replenisher solution and the replenishment tank, so that
It is also possible to realize the conversion of the automatic processing machine.

However, this method is a system in which the powdery processing agent is weighed and charged into the processing tank, and the weighing accuracy is likely to vary. This is because the treatment agents have different specific gravities, and the treatment agent components are biased. Further, the position where the powdery processing agent is set is the upper part of the processing tank, which is in a high humidity environment. Therefore, in this method, it is difficult to completely prevent the powdery treatment agent that has been set from being moisture-proof, and the moisture absorption of the powdery treatment agent causes a decrease in weighing accuracy and a deterioration in storage stability of the treatment agent, which is not perfect.

Further, this patent does not describe any limitation on the unit supply amount of the solid processing agent supplied to the processing tank.

The reason is that if the unit supply amount of the solid processing agent is too large, poor dissolution of the solid processing agent is likely to occur. Particularly when the solid processing agent is a color developing processing agent, a color developing agent having a low solubility is used. Problems such as sticking out will occur. On the contrary, if the unit supply amount of the solid processing agent is too small, the number of times of charging for supplying a certain processing agent amount increases. Originally, in the case of this method in which the weighing accuracy of the solid processing agent is likely to be rounded, the weighing accuracy of the processing agent is further decreased due to the increase in the number of times of loading, which is not preferable. Furthermore, the increase in the number of times of input corresponds to the fact that the solid processing agent housed inside the hopper has more chances to come into contact with the outside air, so a silver halide photographic light-sensitive material that uses many materials that easily absorb moisture. In the case of the treating agent for use, the weighing accuracy is further reduced due to moisture absorption, and insoluble matter is generated due to the deterioration of the preservability of the solid treating agent, resulting in poor dissolution.

Further, in this patent, the range y and the ratio y / x of the mole number y of the color developing agent and the mole number of the carbonate contained in the color developing solid processing agent supplied in unit amounts are limited, and the range is limited. There is no clear statement as to why.

If y / x is too large, the content of the color developing agent is too large, and the color developing agent may be poorly dissolved or stick out. On the other hand, if y / x is too small, the color developing agent is surrounded by an alkaline atmosphere of carbonate at a stretch, and the solubility decreases due to an increase in pH. The color developing agent causes poor dissolution and protrusion. .

That is, in Japanese Patent Application No. 4-237045, the unit supply amount of the color developing solid processing agent for silver halide photographic light-sensitive material to be supplied to the processing tank and the color developing solid processing agent supplied in unit amount are described. By setting both the ratio y / x of the number of moles y of the color developing agent and the number x of carbonates contained in a preferable range, prevention of poor dissolution of the color developing solid processing agent can be achieved. Is not described at all.

Further, JP-A-2-09043 discloses a solid processing agent for granular silver halide photographic light-sensitive materials, and JP-A-4-230748 discloses a silver halide divided into parts in a multilayer structure. Although disclosures have been made regarding color developing solid processing agents for photographic light-sensitive materials, these patents do not directly use the solid processing agents in a processing tank for use, and have a different purpose from the present invention. Is.

The present invention relates to a color developing solid processing agent for a silver halide photographic light-sensitive material, which is characterized in that it is directly charged into a processing tank in an automatic developing machine by a unit supplying amount. And the ratio y / x of the number y of moles of the color developing agent and the number x of moles of the carbonate contained in the solid developing agent for color developing, which are supplied in unit amounts, respectively. The purpose of this invention is to eliminate the work of preliminarily dissolving the replenisher and stabilize the processability without maintenance, and the purpose is different from the above invention. Not something you can do. Therefore, the object of the present invention is, firstly, to eliminate the liquid chemical that poses a risk of transportation and handling and to enable the use of solid chemical without complicated operations for the user. To supply a processing agent for photosensitive materials.

Secondly, it is to supply the processing agent for silver halide photographic light-sensitive material which has completed the fully automatic replenishment system by eliminating the dissolution work of the concentration kit by the user himself.

Thirdly, it is necessary to eliminate many built-in replenishing tanks and supply a compacted processing agent for silver halide photographic light-sensitive materials.

The fourth object is to supply a processing agent for a silver halide photographic light-sensitive material, which improves processing stability by eliminating the need for storing a liquid replenisher and reduces the amount of chemical waste liquid.

The fifth object is to supply a processing agent for silver halide photographic light-sensitive materials which achieves a low-pollution system in which the use of plastic packaging materials for liquids is eliminated and the use of plastic packaging materials is reduced.

The sixth object is to supply a solid developing agent for color developing for silver halide photographic light-sensitive materials, which achieves prevention of dissolution failure of the solid processing agent to be replenished and has greatly improved processing stability.

[0053]

It has been found that the above object of the present invention can be achieved by any one of the following constitutions.

Having at least one water-soluble group
In a solid developing agent for color developing for silver halide photographic light-sensitive materials, which contains a p-phenylenediamine compound and a carbonate, and is directly supplied to the processing tank in the automatic developing machine in unit-supplying amounts. The ratio y / x of the number of moles y of the p-phenylenediamine compound and the number x of moles of the carbonate in the color developing solid processing agent is 0.092 ≦ y / x ≦ 0.5, and the color developing A solid developing agent for color development for silver halide photographic light-sensitive materials, characterized in that the unit supply amount of the solid processing agent is 0.5 to 50 g.

The silver halide photographic light-sensitive material according to the above item, wherein the solid developing agent for color development for silver halide photographic light-sensitive material is a granule formed by a granulation step or a tablet formed by tableting. Solid developer for color development.

The color developing solid processing agent for a silver halide photographic light-sensitive material as described in the above item, wherein the color developing solid processing agent for a silver halide photographic light-sensitive material is divided and weighed in a predetermined amount in advance.

[0057]

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

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

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

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

The present invention will be described in more detail below.

Among the above color developing solid processing agents, granules or tablets are preferably used because of high replenishment accuracy and easy handling.

To solidify the photographic processing agent, a concentrated liquid or fine powder or granular photographic processing agent and a water-soluble binder are kneaded and molded, or a water-soluble binder is preliminarily formed on the surface of the photographic processing agent. Any means such as forming a coating layer by spraying can be adopted (Japanese Patent Application No. 2-135887, No. 2-203165,
2-203166, 2-203167, 2-203168, 2-304
See No. 09).

A preferred method for producing tablets is a method in which a solid processing agent in powder form is granulated and then a tableting step is performed. There is an advantage that the solubility and storability are improved and the photographic performance becomes stable as compared with the solid type processing agent formed by the tableting process by simply mixing the solid processing agent components.

As the granulation method for tablet formation, known methods such as tumbling granulation, extrusion granulation, compression granulation, crushing granulation, stirring granulation, fluidized bed granulation and spray drying granulation are used. Can be done.
For tablet formation, the average particle size of the obtained granules is 100-800 μm, in that when the granules are mixed and compressed under pressure, non-uniformity of the components, so-called segregation is unlikely to occur. It is preferable to use one, more preferably 200 to 750 μm
Is. Furthermore, the particle size distribution is ± 10 for 60% or more of the granulated particles.
Those within a deviation of 0 to 150 μm are preferred. The obtained granulated product is used as it is as granules. When compressing the obtained granulated product under pressure, a known compressor such as a hydraulic press, a single-shot tableting machine, a rotary tableting machine, or a preketching machine can be used. The solid processing agent obtained by compression under pressure can have any shape, but from the viewpoint of productivity, handleability, or from the problem of dust when used on the user side, a cylindrical type, a so-called tablet is used. preferable.

More preferably, at the time of granulation, the above-mentioned effects become more remarkable by separately granulating each component, for example, an alkali agent, a reducing agent, a bleaching agent, a preservative and the like.

A method for producing a tablet treating agent is described in, for example, Japanese Patent Application Laid-Open No.
51-61837, 54-155038, 52-88025, British patent 1
It can be produced by a general method described in the specification such as 213808, and further, the granule treating agent is, for example, JP-A-2-09042,
It can be produced by a general method described in the specifications such as 2-109043, 3-39735 and 3-39739. Further, the powder processing agent is, for example, JP-A-54-133332, British Patent 725892.
No. 729862, and German Patent No. 3738361, and the like.

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

The black and white developing agents, color developing agents, bleaching agents, bleach-fixing agents and stabilizers can be excluded from the regulation of liquid dangerous substances.

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

It is within the scope of the present invention to solidify only one part of a certain treating agent in the solid treating agent used in the present invention, but preferably all components of the treating agent are solidified. is there. It is desirable that each component be molded as a separate solid processing agent and packaged in the same manner. It is also desirable that the individual components are packaged in the order in which they are periodically added repeatedly in a package.

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

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

As the color developing agent used in the color developing solution in the present invention, a p-phenylenediamine compound having a water-soluble group is preferably used.

Examples of the water-soluble group include those having at least one amino group of the p-phenylenediamine compound or on the benzene nucleus. Specific water-soluble groups include-(C
_{H 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'Cm'H 2
m ′ ₊₁ (m ′ and n ′ each represent an integer of 0 or more) —COOH group, —SO ₃ H group and the like are preferable.

Specific examples of the color developing agent preferably used in the present invention are shown below.

[0077]

[Chemical 1]

[0078]

[Chemical 2]

[0079]

[Chemical 3]

Of the above-illustrated color developing agents, particularly preferred in the present invention are exemplified compounds (1), (3),
(18).

The carbonate in the present invention is potassium carbonate,
It is supplied by using sodium carbonate, potassium hydrogen carbonate, or sodium hydrogen carbonate alone or in combination.

In the description of the present invention, the "unit supply amount" refers to the total weight of the solid color forming processing agent which is directly charged into the processing tank according to a certain processing amount of the light-sensitive material.

Here, the above-mentioned processing tank refers to a portion in which a processing liquid for actually processing the photosensitive material is circulated, and it may be a position near the processing rack or a sub tank in which a filter is set.

The inventors of the present invention provide a color developing solid processing agent for silver halide photographic light-sensitive material, which is characterized in that a unit supply amount is directly fed to a processing tank in an automatic developing machine. Supply amount and the number of moles of color developing agent contained in the color developing solid processing agent that is supplied in unit amount y
It has been found that, by supplying the color developing solid processing agent in which both the ratio y / x of the number of moles of the carbonate and the number x of carbonates are set in preferred ranges, it is possible to prevent the solid color developing processing agent from being poorly dissolved.

In the present invention, the number of moles of the color developing agent contained in the solid developer of the color developing solution supplied in unit amounts y
It has been found that the ratio y / x of the number of moles of carbonate to x is preferably 0.092 ≦ y / x ≦ 0.5, and more preferably 0.095 ≦ y ≦ 0.4, in order to produce the effects of the present invention described above. It was

In the present invention, the unit amount of the color developing solid processing agent fed at one time is preferably 0.5 to 50 g, and more preferably 1 to 30 g in order to produce the effects of the present invention. Was found. Here, the color developing solid processing agent to be added at one time may be divided into, for example, an alkali part, a main agent part, or the like, or may be collectively included. As a method for supplying the solid processing agent to be charged at one time, a method may be used in which it is weighed each time when it is charged into the processing tank, or a method in which the solid processing agent is tableted and dropped one by one. Alternatively, the unit supply amount may be weighed in advance, each of the weighed solid processing agents may be individually packaged, and the solid processing agent may be supplied while the packaging is opened. However, in consideration of the moistureproofness of the solid processing agent, the latter method of individually packaging the previously divided and weighed solid processing agents and supplying the solid processing agent while opening is more preferable.

The moisture-proof packaging of the solid processing agent can be carried out using the following materials.

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

These films are usually laminated and adhered to each other, but may be applied as a coating layer.

Further, it is more preferable to use various gas barrier films such as using aluminum foil or aluminum vapor-deposited synthetic resin between the above synthetic resin films.

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

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

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

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

Next, as the laminated polymer resin film which meets the conditions of the present invention, for example, (4) PET / polyvinyl alcohol / ethylene copolymer (Eval) / polyethylene (PE), (5) stretched polypropylene ( OPP) / Eval / PE, (6) Unstretched polypropylene (CPP) / Eval / PE, (7) Nylon (N) / Aluminum foil (Al) /
PE, (8) PET / Al / PE, (9) cellophane / PE
/ Al / PE, (10) Al / paper / PE, (11) PET / PE
/ Al / PE, (12) N / PE / Al / PE, (13) paper / P
E / Al / PE, (14) PET / Al / PET / polypropylene (PP), (15) PET / Al / PET / high density polyethylene (HDPE), (16) PET / Al / PE / low density polyethylene (LDPE) ), (17) Eval / PP,
(18) PET / Al / PP, (19) paper / Al / PE, (20) P
E / PVDC Coated Nylon / PE / Ethyl Vinyl Acetate Polyethylene Condensate (EVA), (21) PE / P
VDC coat N / PE, (22) EVA / PE / aluminum deposited nylon / PE / EVA, (23) aluminum deposited nylon / N
/ PE / EVA, (24) OPP / PVDC coat N / P
E, (25) PE / PVDC coat 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, (31) OPP / CPP, (32)
OPP / LDPE, (33) OPP / HDPE, (34) OPP
/ N / CPP, (35) OPP / Uniaxially stretched nylon / LDP
E, (36) OPP / PET / CPP, etc., among which (20) to (36) are preferably used.

As a more specific constitution of the packaging material, if the side in contact with the treating agent is the inner surface, PE / mainly paperboard / PE / Al / epoxy-phosphoric acid resin layer / polyester resin in this order from the inner surface. Layer / PE PE / K-nylon / PE or adhesive / Al / PE /
Paperboard / PE PE / vinylon / PE or adhesive / Al / PE / paperboard / PE PE / vinylidene chloride / PE or adhesive / Al / PE
/ Paperboard / PE PE / Polyester / PE or Adhesive / Al / PE /
Paperboard / PE Polypropylene / K-Nylon / Polypropylene / Al
/ Polypropylene / paperboard / polypropylene etc.

As a method for moisture-proof packaging of the solid processing agent, there are 4-way seal, 3-way seal stick (pillow package, gusset package) and PTP (blister package) cartridge.

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

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

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

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

Further, the delamination method is one in which the sealant is peeled between the layers of the laminate film by using a multilayer coextrusion film such as a laminate film.

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

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

Examples of the sealant film include Tohcello, CMPS film, Dainippon Ink Diffran PP-100 and PS-300, or letterpress printing LTS film.
There are Sanseal FR, Sunseal MS, etc. manufactured by San-A Chemical Co., Ltd., and Declan C-1600T, C-1602T and the like are types already laminated with polyester.

PTP is a packaging form in which a solid processing agent is put into a sheet of PVC, CPP or the like which is molded as a kind of blister packaging and heat sealed with an aluminum sealing material.

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

When the treatment agent is packaged in a water-soluble film,
Water-soluble films are polyvinyl alcohol-based, methyl cellulose-based, polyethylene oxide-based, starch-based,
Polyvinylpyrrolidone type, hydroxypropyl cellulose type, pullulan type, dextran type and gum arabic type, polyvinyl acetate type, hydroxyethyl cellulose type, carboxyethyl cellulose type, carboxymethyl hydroxyethyl cellulose sodium salt type, poly (alkyl) oxazoline type, polyethylene glycol type Films composed of the above base materials are preferably used, and among these, polyvinyl alcohol-based and pullulan-based films are particularly preferably used.

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

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

Further, as these water-soluble films, those commercially available under the names of Solbron (manufactured by Aicello Chemical Co., Ltd.), Hi-Selon (manufactured by Nigo Film Co., Ltd.) or Pullulan (manufactured by Hayashibara Co., Ltd.) can be used. Also, Chris Craft Industries Inc.
7000 series polyvinyl alcohol film, available from MONO-SOL Division, dissolves at water temperatures of about 34 ° F. to about 200 ° F., is harmless and exhibits a high degree of chemical resistance, and is particularly preferably used. .

The thickness of the above water-soluble film is preferably 10 to 120 μ, particularly 15 to 80 μ from the viewpoints of storage stability of the solid processing agent, dissolution time of the water-soluble film and crystal precipitation in an automatic processor. Preferred, especially 20
Those having a size of -60 μm are preferably used.

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 excellently achieved.

Further, 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 × 1
0 ⁶ kg / m ² is preferred, especially 1.5 × 10 ⁶ to 10 × 10 ⁶ k
g / m ² is preferred. These tensile strengths are measured by the method described in JIS Z-1521.

Further, in the practice of the present invention, it is also preferable that the moisture-proof packaging material is a degradable plastic, particularly a biodegradable or photodegradable plastic.

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

The specific representative examples are as follows.

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

Examples of the photodegradability include the introduction of a carbonyl group for photodisintegration, and the addition of an ultraviolet absorber to accelerate the disintegration.

Regarding such degradable plastic,
"Science and Industry" Vol. 64, No. 10, pp. 478-484 (1990),
The materials generally described in "Functional materials", July 1990, pp. 23-34, can be used. In addition, Biopol (manufactured by ICI), Eco (manufactured by Union Carbide), Ecolite (manufactured by Eco Plastic), Ec
Commercially available disassembled plastics such as ostar (St. Lawrence Starch) and Knuckle P (Nihon Unicar) can be used.

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

In the present invention, the method for supplying the solid processing agent to the processing tank is, for example, as a supplying means for supplying the solid processing agent to the processing tank, for example, a predetermined amount of the solid processing agent previously weighed and divided and packaged is used as the photosensitive material. This is a system in which the package is opened and removed according to the processing amount of.

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

As another embodiment, it is conceivable that a part of the seal package for packaging the solid processing agent is provided with a notch and the package portion not containing the solid processing agent is pulled to open the package. . As another embodiment, it is possible to open the package by cutting a part of the seal package for individually packaging the solid processing agent by an external force with a cutter or the like.

As another embodiment, a mode in which the package body is pulled in two directions so that the sealed portion of the sealed package body for packaging the solid processing agent is peeled off and the package is opened can be considered.

As another embodiment, it is conceivable that at least one of the packaging bodies made of at least two packaging materials can be opened by an external force so as to sandwich the solid processing agent. As an unsealing method, for example, a method such as a PTP method in which the solid processing agent is forcibly pushed out by applying a compressive force from the non-opening side packaging body through the solid processing agent in the direction of the openable packaging body is considered. .

The solid color-developing agent of the present invention includes Japanese Patent Application No. 2-21
The solid compound and the optical brightener described in No. 8720, pages 11 to 38 can be contained.

In the present invention, the solid processing agent is divided and weighed into a predetermined amount and a fixed amount in advance. Therefore, the processing in the automatic processor of the present invention has high replenishment accuracy and exhibits extremely stable continuous processing performance. Pre-divided weighing means that the processing agent is already weighed in a predetermined amount before being stored in the automatic developing machine or before the packaging material containing the processing agent is set in the fixing means. For example, it refers to a mode in which tablets or pills having a predetermined size are formed, and a mode in which granules or powders are subdivided into predetermined amounts and packaged. It does not include a mode in which the powder or granules are put in the storage means and the amount of each input is measured at the time of supply.

In the conventional replenisher supply replenishment system, replenishment is performed by a bellows pump, but the accuracy of this pump is not constant and is not suitable for precise replenishment control. On the other hand, the solid processing agent in the case of the present invention is produced by being weighed and divided into a fixed amount at a processing agent production factory, for example, and the replenishment control is ON / OFF control whether the solid processing agent is fed or not. There is no variation due to. Therefore, the accuracy of supplying the processing agent is remarkably high, and the stable processing performance can be obtained also by this. The solid processing agent of the present invention includes powder, granules, tablets,
Any of pills and the like may be used, and there is no problem in mixing these.

[0130]

【Example】

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

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

The alternate long and short dash line in the figure indicates the transport path of the silver halide photographic light-sensitive material. In the embodiment, the light-sensitive material is introduced into the automatic developing machine A in a cut state, but it may be introduced into the automatic developing machine in the form of a strip. In that case, if an accumulator for temporarily retaining the photosensitive material is provided between the automatic developing machine A and the photoprinting machine B, the processing efficiency is improved. Further, it goes without saying that the automatic developing machine according to the present invention may be configured integrally with the photo printing machine B or may be a single automatic developing machine. Needless to say, the silver halide photographic light-sensitive material processed by the automatic developing machine according to the present invention is not limited to exposed photographic paper, and may be exposed negative film or the like. Also,
The present invention will be described with respect to a developing machine having substantially three tanks including a color developing tank, a bleach-fixing tank, and a stabilizing tank, but the present invention is not limited to this, and the color developing tank, the bleaching tank, the fixing tank, The present invention can be applied even to an automatic developing machine having a substantially 4-tank structure having a stabilizing tank.

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

The processing tank 1 is a processing section 2 for processing a photosensitive material.
And a solid processing agent feeding section 11 for supplying the tablets 13 integrally provided on the outside of the partition wall forming the processing section. The processing section 2 and the solid processing agent feeding section 11 are partitioned by a partition wall 12 having a communication window formed therein, so that the processing solution can flow. Further, since the charging section 11 is provided with the section 14 for receiving the processing agent, it does not move to the processing section 2 in a solid state.

The cylindrical filter 3 is a solid processing agent charging section.
It is provided below 11 so as to be replaceable, and has a function of removing insoluble matter such as paper waste in the processing liquid. In the filter 3, a circulation pump 5 (circulation means) is provided through a circulation pipe 4 provided through the lower wall of the solid processing agent feeding portion 11.
It communicates with the suction side of.

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

The drainage pipe 6 is for overflowing the processing liquid in the processing section 2, and keeps the liquid surface level constant, as well as components brought in by adhering to the photosensitive material from another processing tank, The components leaching from the photosensitive material are stored,
Helps prevent the increase.

The rod-shaped heater 7 is arranged so as to penetrate the upper wall of the solid processing agent feeding part 11 and be immersed in the processing liquid in the solid processing agent feeding part 11. This heater 7 is used in the processing tank 1
It heats the processing liquid inside, in other words, processing tank 1
Temperature range suitable for processing the processing liquid inside (eg 20-55 ℃)
It is a temperature adjusting means that is held at.

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

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

The tablets 13 stored in the cartridge 15 are shown in FIG.
The seal package is individually packaged by the seal package shown in (1), and the seal package containing the tablets 13 ejected from the cartridge 15 by the opposed rotor 17b is cut by the cutter 17a. Due to gravity, the tablets 13 are put into the filtering section (section) 14 from the opened seal package.

The processing agent supply means 17 (see FIG. 6 for a detailed diagram).
7) is controlled by the processing agent supply control means 9 to be described later, and in conjunction with the supply signal issued from the processing agent supply control means 9, the tablets 13 are placed in the solid processing agent input part 11 as shown in FIG. To the filtering section (section) 14. In the present invention, the solid processing agent is supplied to the filtering section (section) 14 in the solid processing agent receiving section 11 as shown in FIG. That is, in the present invention, it suffices that the processing solution can be used to dissolve the solid processing agent, and the components corresponding to the processing amount information of the photosensitive material are surely added, and the processing characteristics of the processing solution in the processing tank 1 are kept constant. However, it is more preferable that the solid processing agent is supplied into the circulation path of the processing solution. Also,
It is preferable that the treatment agent supply means 17 is configured so that moisture in the treatment tank of the automatic developing machine or moisture in the outside air, or scattered treatment liquid does not come into contact with the solid treatment agent before being supplied to the treatment tank. .

The filtering section (section) 14 is the solid processing agent feeding section 11
An insoluble component of the tablet 13 which is dipped in the treatment liquid inside and is supplied by the treatment agent supplying means 17, for example, an insoluble component mixed in the tablet 13, a tablet 13 formed by disintegrating the tablet 13
It is intended to remove not only tablets 13 but also solid processing agent-derived lumps, etc. that may damage the finished image or cause insufficient processing of the adhered areas, such as tablets 13. is there. The filtering part (section) 14 is made of resin. Note that it is not essential to provide the filtering section (section) 14 in the solid processing agent feeding section 11, and the tablets 13 supplied by the processing agent supplying means 17 are the photosensitive material transport paths shown in FIG. 1 or the processing section. It may be added to the treatment liquid in No. 2.

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

The replenishing water supply means (a) is a replenishing water (replenishing water) from the replenishing water tank 43 for storing the replenishing water to the solid processing agent feeding section 11.
And a hot water supply device including a pump, a temperature controller, etc., a solenoid valve, and a water supply pipe. The replenishing water supply means (a) is for supplementing the water taken out by the photographic material and the water evaporated from the tank surface, while diluting the cumulative control component eluted by the reaction. In the figure, reference numeral 23 denotes evaporative replenishment water setting means.

FIG. 3 is a schematic plan view showing the automatic developing machine A of FIG. 1 from the top (however, for explanation, the route of the water replenishing means is described). Reference numeral 32 is a hot water supply device, 33 is a solenoid valve, and 36 is a rehydration pipe. FIG. 4 is a block diagram relating to the control according to this example. FIG. 4 is a block diagram in which a pre-programmed evaporative replenishment water setting means 23 is added to the control means.
Incidentally, FIG. 3 shows a replenishing water tank 43 for storing replenishing water. Further, in this example, a case where tablets are used as the solid processing agent will be described.

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

This replenishment water control means controls and / or processes the replenishment water supply means 42 by the evaporation replenishment water setting means 23 (FIG. 4) which is programmed in advance by the environmental temperature and humidity (relative humidity) of the installation place. It is a control means for controlling the replenishment water supply means 42 according to the processing amount information and the like detected by the amount information detecting means 8. The supplementary water supply control means
The control is not limited to the processing amount information detected by the processing amount information detecting means 8, and may be controlled according to the information that the processing agent is supplied by the processing agent supplying means 17.

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 (FIG. 1). The processing agent supply control means 9 supplies a processing signal to the processing agent supply means 17 when the accumulated area of the photosensitive material to be processed reaches a predetermined area in accordance with the processing amount information detected by the processing amount information detecting means 8. Emit. Upon receiving the supply signal, the processing agent supply means 17 is a cartridge by the opposed roller 17b.
Cutter the three-sided seal packaging containing 13 tablets carried from 15
17a is cut, and the tablets 13 are supplied to the filtering section (section) 14 in the solid processing agent feeding section 11 by gravity. Tablets supplied 13
Is dissolved by the processing liquid in the solid processing agent input section 11, but the processing is circulated by the circulation means in the order of the solid processing agent input section 11 → circulation pump 5 → processing section 2 → communication window → solid processing agent input section 11. Dissolution is accelerated by the liquid.

Simultaneously with the above operation, the replenishing water supply means (a) receives a signal from the replenishing water amount setting set 23, and the replenishing water is supplied to the treatment tank. On the other hand, the detected light-sensitive materials are the color developing tank 1A, the bleach-fixing tank 1B, the stabilizing tanks 1C, 1D and 1E.
The inside is sequentially conveyed by the roller conveying means (see automatic developing machine A in FIG. 1). The color developing tank 1A, which is a processing tank,
Bleach-fixing tank 1B, stabilizing tanks 1C, 1D, 1E,
The processing agent supply means 17 may be provided and may be supplied simultaneously. Further, the timings supplied by the respective supply means may be different from each other, and further, the area of the predetermined photosensitive material to be processed for controlling the processing agent supply means by the processing agent supply control means 9 is: Each processing tank 1A, 1B,
It is needless to say that 1C, 1D, and 1E may be the same, but may be different from each other.

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

Continuous processing was performed in the processing steps shown in Table 1 below using the automatic processor. As the color paper to be treated, QA paper type A5 manufactured by Konica was used.

[0153]

[Table 1]

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

Further, the evaporation correction is carried out at the time of temperature control by color development, bleach-fixing, and stably 9.0 ml / hour, 7.2 ml / hour, 14.1 ml / hour, respectively, every hour, and when temperature control is not performed. , 3.
8 ml / hour, 3.1 ml / hour, 6.1 ml / hour were integrated and the temperature was adjusted at the beginning.

The tank liquid at the start is Konica Color Q
A paper color development starter 28P-1B, (Konica Color QA Paper bleach-fix starter 28P-2B manufactured by Konica Corporation)
(Same as above), Konica Color QA Paper Stable Starter 28P-
It was created using 3B (same as above).

Next, the following color paper treating agent was prepared.

(1-1) Powder developing agent for color developing replenishment for color paper Exemplified compound of developing agent (1) Amount described in Table 3, disulfoethylhydroxylamine disodium salt 120 g, Tinopearl SFP (manufactured by Ciba Geigy) 30 g, Sodium sulfite
3.7 g, potassium bromide 0.3 g, diethylenetriamine pentaacetic acid 25 g, sodium p-toluenesulfonate 280 g, potassium hydroxide 20 g, and potassium carbonate 330 g were ground in a commercially available bandam mill to an average particle size of 10 μm, and these materials were used. Was mixed uniformly for 10 minutes using a mixer in a room where the humidity was controlled to 40% RH or less, and this was divided into unit supply amounts shown in Table 3 to prepare a color paper color development replenishing powder processing agent (1). did.

(1-2) Granular processing agent for replenishing color development for color paper Operation (A) Exemplified compound of developing agent (1) Grinded amounts shown in Tables 3 and 4 in a commercially available bandam mill until the average particle size became 10 μm. To do. 50 minutes of this fine powder at room temperature in a commercial stirred granulator
After granulating by adding ml of water, the granulated product is dried at 40 ° C. for 2 hours in a fluidized bed dryer to almost completely remove the water content of the granulated product for replenishing color development for color paper. A granule treating agent (A) was prepared.

Operation (B) Disulfoethylhydroxylamine disodium salt 120
Then, g is pulverized and granulated in the same manner as in the operation (A). How much water is added
After granulating to 6.0 ml, the granulated product was dried at 50 ° C. for 30 minutes to almost completely remove water from the granulated product to prepare a granule processing agent (B) for color development replenishment for color paper.

Operation (C) 30.0 g of Tinopearl SFP (manufactured by Ciba Geigy), 3.7 g of sodium sulfite, 0.3 g of potassium bromide, 25 g of diethylenetriamine-5-acetic acid, sodium p-toluenesulfonate 28
After crushing 0 g, 20 g of potassium hydroxide and 10.6 g of mannitol in the same manner as in (A), they are uniformly mixed with a commercially available mixer. Then, in the same manner as in (A), the amount of water added is adjusted to 20 ml and granulation is performed. After the granulation, the granulated product was dried at 60 ° C. for 30 minutes to almost completely remove the water content of the granulated product to prepare a granule processing agent (C) for color development replenishment for color paper.

Operation (D) 330 g of potassium carbonate is ground and granulated in the same manner as in the operation (A). The amount of water added was 20 ml, and after granulation, the granules were dried for 30 minutes at 700 ° C. to almost completely remove the water content, to prepare a color development replenishing granule processing agent (D) for color paper.

The above-mentioned color development replenishing granule processing agents (A) to (D) for color paper were mixed in a ratio of the total weight of each granule, and the mixture was divided into unit supply amounts shown in Tables 3 and 4 for color paper. It was used as a granule processing agent (2) for replenishing color development.

(1-3) Tablet processing agent for color development replenishment for color paper Operation (A ') Exemplified compound of developing agent (1) The amount shown in Table 4 is ground in a commercially available bandam mill until the average particle size becomes 10 μm. . This fine powder was granulated in a commercial stirred granulator at room temperature for about 7 minutes by adding 50 ml of water, and then the granulated product was dried in a fluidized bed dryer at 40 ° C. for 2 hours. The water content of the granulated product is almost completely removed. In this way, 40 g of polyethylene glycol 6000 is mixed uniformly with the prepared granulated product for 10 minutes using a mixer in a room where the humidity is adjusted to 25 ° C. and 40% RH or less. next
After adding 1 g of sodium N-lauroylalanine and mixing for 3 minutes, the resulting mixture was mixed with a tableting machine which was modified from Tuffpress Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd.
The tablet was compressed to an appropriate amount per tablet to give a color development replenishing tablet (A ') for color paper.

Procedure (B ') Disulfoethylhydroxylamine disodium salt 120
Similarly to the operation (A '), g is pulverized and granulated. The amount of water added is 6.0 ml, and after granulation, the granules are dried for 30 minutes to remove almost completely the water content. In this way, N-lauroylalanine sodium 4 was added to the prepared granules,
Use a mixer in a room that has been conditioned at 25 ℃ and 40% RH or less 3
Mix for minutes. Next, the obtained mixture was compressed into tablets having a proper filling amount per tablet with a tableting machine which was modified from Tough Pressed Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd. to give tablets for color development replenishment for color paper (B '). )made.

Operation (C ') 30.0 g of Tinopearl SFP (manufactured by Ciba-Geigy), 3.7 g of sodium sulfite, 0.3 g of potassium bromide, 25 g of diethylenetriamine-5-acetic acid, sodium p-toluenesulfonate 28
After crushing 0 g, 20 g of potassium hydroxide and 10.6 g of mannitol in the same manner as in (A), they are uniformly mixed with a commercially available mixer. Then, in the same manner as in (A), the amount of water added is adjusted to 20 ml and granulation is performed. After the granulation, the granulated product is dried at 60 ° C for 30 minutes to almost completely remove the water content of the granulated product. In this way, 4 g of sodium N-lauroylalanine was added to the thus-prepared granulated product, and mixed for 3 minutes using a mixer in a room where the humidity was controlled to 25 ° C. and 40% RH or less. Next, the obtained mixture was compressed into tablets using a tableting machine modified from Tough Pressed Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd., in an amount corresponding to the appropriate amount of filling per tablet.
A color development replenishing tablet (C ') for color paper was prepared.

Operation (D ') 330 g of potassium carbonate is pulverized and granulated in the same manner as in the operation (A'). The amount of water added is 20 ml, and after granulation, the granules are dried for 30 minutes to remove water almost completely. In this way, polyethylene glycol 6000 was added to the adjusted granules.
15 g of the mixture is uniformly mixed for 10 minutes using a mixer in a room whose humidity is adjusted to 25 ° C. and 40% RH or less. Next, 4 g of sodium N-lauroylalanine was added and mixed for 3 minutes, and the obtained mixture was tough pressed collect 1527 manufactured by Kikusui Seisakusho KK
A tableting machine with a modified HU was used to perform compression tableting with an appropriate amount of filling per tablet to prepare color development replenishing tablets (D ') for color paper.

The above-mentioned appropriate dose means each tablet (A ') to
The weight ratio of (D ') was made equal to the total weight ratio of each granule, and the total amount of tablets (A') to (D ') was controlled to be the unit supply amount shown in Table 4.
Color development replenishing tablet (A ′) for color paper
(D ') One by one was combined to form a color developing replenishing tablet (3) for color paper.

(1-4) Tablet-like processing agent for color developing replenishment for color paper Operation (A ″) Exemplified compound of developing agent (1) The amount shown in Table 5 is ground in a commercially available bandam mill until the average particle size becomes 10 μm. After granulating this fine powder in a commercial stirred granulator at room temperature for about 7 minutes by adding 50 ml of water, the granulate is dried in a fluid bed dryer at 40 ° C. for 2 hours. In this way, 40g of polyethylene glycol 6000 was added to the adjusted granules in a room where the humidity was adjusted to 25 ° C and 40% RH or less using a mixer. The mixture was uniformly mixed for a minute to prepare a granule (A ″) for color development replenishment for color paper.

Procedure (B ″) Disulfoethylhydroxylamine disodium salt 120
Grain and granulate in the same manner as in step (A ″). Add water to 6.0 ml, and after granulation, dry at 50 ° C for 30 minutes to almost completely remove the water content of the granules. A granule (B ″) for color development replenishment for paper was prepared.

Operation (C ″) 30.0 g of Tinopearl SFP (manufactured by Ciba Geigy), 3.7 g of sodium sulfite, 0.3 g of potassium bromide, 25 g of diethylenetriamine-5-acetic acid, sodium p-toluenesulfonate 28
After crushing 0 g, 20 g of potassium hydroxide and 10.6 g of mannitol in the same manner as in (A ″), they are uniformly mixed in a commercially available mixer. Then, in the same manner as in (A ″), the amount of water added is 20 ml. Granulate. After the granulation, the granulated product was dried at 60 ° C. for 30 minutes to almost completely remove the water content of the granulated product to prepare a color developing replenishing granule (C ″) for color paper.

Operation (D ″) 330 g of potassium carbonate is crushed and granulated in the same manner as in the operation (A ″). The amount of water added is 20 ml, and after granulation, the granules are dried for 30 minutes to remove water almost completely. In this way, polyethylene glycol 6000 was added to the adjusted granules.
15 g was uniformly mixed for 10 minutes using a mixer in a room whose humidity was controlled to 25 ° C. and 40% RH or less to prepare a color developing replenishing granule (D ″) for color paper.

The respective granules (A ″) to (D ″) were mixed in a ratio of total weight, and the total amount of the respective granules (A ″) to (D ″) became the unit supply amount shown in Table 5. Control unit, 0.5% by weight of the unit supply amount of sodium N-lauroylalanine was added, and the mixture was mixed for 3 minutes. The obtained mixture was manufactured by Kikusui Seisakusho Co., Ltd. Tough Pressed Collect 1527.
Compression tableting was carried out using a tableting machine with a modified HU to obtain granules (4) for color development replenishment for color paper.

2) Bleach-fixing replenishing tablet for color paper Operation (E) Diethylenetriamine pentaacetic acid ferric ammonium monohydrate
1250g, ethylenediamine tetraacetic acid 25g, maleic acid 250
46 g of Pine Flow (Matsuya Chemical Co., Ltd.) are pulverized, mixed and granulated in the same manner as in the operation (C). The amount of water added is 80 ml, and after granulation, the granules are dried for 2 hours to almost completely remove the water content. In this way, 15 g of N-lauroyl sarcosine sodium was added to the prepared granules, and the temperature was 25 ° C and 40% RH.
Mix for 3 minutes using a mixer in a conditioned room below. Next, the resulting mixture was compressed into tablets with a tableting machine modified from Tough Pressto Correct 1527HU manufactured by Kikusui Seisakusho Co., Ltd. with a filling amount of 8.6 g per tablet, and bleach-fixing replenishment for 170 color papers. Tablet A for tablets was prepared.

Operation (F) Ammonium thiosulfate 1640 g, sodium sulfite 750
g, 40 g of potassium bromide and 50 g of p-toluenesulfinic acid are pulverized, mixed and granulated in the same manner as in the operation (C). The amount of water sprayed is 100 ml, and after granulation, it 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-lauroylsarcosine is added to the prepared granulated product, and the mixture is mixed for 3 minutes using a mixer in a room whose humidity is adjusted to 25 ° C. and 40% RH or less. Next, the resulting mixture is used by Kikusui Seisakusho.
Using a tableting machine modified from Tough Presto Correct 1527HU manufactured by Co., Ltd., compression tableting was carried out with the filling amount per tablet being 13.4 g, to prepare 170 tablets of bleach-fixing supplement tablet B for color paper.

The above bleach-fixing replenishing tablets for color paper (E) and (F) were combined to prepare a bleach-fixing replenishing tablet for color paper.

3) Tablets for stable replenishment of color paper Sodium carbonate monohydrate 10 g, 1-hydroxyethane-1,1
-Disodium diphosphonate 200g, Tinopearl SFP15
In the same manner as in the operation (C), 0 g, 300 g of sodium sulfite, 20 g of zinc sulfate heptahydrate, 150 g of ethylenediaminetetraacetic acid disodium, 200 g of ammonium sulfate, 10 g of o-phenylphenol, and 25 g of pine flow are pulverized, mixed and granulated. The amount of water added is 60 ml, and after granulation, it is dried at 70 ° C. for 60 minutes to almost completely remove the water content of the granulated product. In this way, 10 g of sodium N-lauroyl sarcosine was added to the granules prepared.
Is added, and the mixture is mixed for 3 minutes by using a mixer in a room whose humidity is controlled to 25 ° C. and 40% RH or less. Next, the resulting mixture was compressed into tablets with a tableting machine modified from Tough Pressed Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd. with a filling amount of 3.1 g per tablet for stable replenishment of 360 color papers. The tablets were made.

The solid processing agent was three-way sealed and packaged with a stretched polypropylene / unstretched polypropylene film having a thickness of 60 μm.

On the other hand, as a comparative example, the replenishing tank was charged with the powder solid color developing agent required amount (1) of the present invention (1) and the replenishing water corresponding thereto to prepare 10 liters of replenishing solution, and the replenishing solution was continuously added in a usual replenishing method. Processed. The replenishment amount of each replenisher is shown in Tables 2, 3, 4, and 5.

As another method of supplying the processing agent, the color developing processing agent (2) for replenishing the granules is packed into the hopper of the powder supply apparatus shown in FIG. 8 at once without being separately packaged, and the necessary amount is weighed. The continuous treatment was carried out by the method of supplying it to the treatment tank. Table 3 shows the amount of the solid processing agent to be weighed.
Described in.

At this time, with respect to the granules for color development replenishment, the granules obtained by the above-mentioned operations (A) to (D) were not mixed, but filled in the hopper of FIG. 8 as a separate part.

Further, as another processing agent supply system, FIG.
The above-mentioned color development replenishing tablet (4) was filled in the tablet supply device shown in 10 and 11, and continuous processing was performed. The size of the tablet filling cartridge shown in FIGS. 10 and 11 was changed according to the supply amount of the processing agent shown in Table 5.

(In FIG. 10, 101 is a processing tank, 102 is a constant temperature tank, 120 is a solid processing agent feeding section, 130 is a solid processing agent replenishing device, 131 is a processing amount information detecting means, and 132 is a processing amount. Supply control means, 133 is a storage container, and in FIG. 11, 133 is a storage container, 331 is a container body, 332 is a guide pin, 333 is a cap member, 333B is an identification protrusion (a loading prevention pin), 334 Is a slide lid, J1A to J5A, J10A are tablets, J1B is a tablet, J1C is a tablet, and J1D is a tablet.) The amount of replenishing water supplied to the treatment tank is shown in Tables 2, 3, 4, and 5.

The processing was carried out with 5 m ^{2 of} color paper per day until the overflow amount became twice as much as the tank solution, and then the state of the color development processing tank was observed, and the sample exposed to the wedge was developed to obtain a blue solution. The maximum reflection density was measured.

The state of the color developing tank was evaluated according to the scale shown below.

◯: There is no insoluble matter Δ: Insoluble matter can be visually confirmed ×: A large amount of insoluble matter exists XX: The filter is clogged by the insoluble matter and the circulation pump does not operate.

The results are shown in Tables 3, 4 and 5.

[0188]

[Table 2]

[0189]

[Table 3]

[0190]

[Table 4]

[0191]

[Table 5]

As is clear from Tables 3, 4 and 5, the unit supply amount of the solid color developing treatment agent is set to 0.5 to 50 g, and the exemplary compounds contained in the solid color developing treatment agent are supplied in unit amounts. By setting the ratio y / x of the number of moles y of (1) and the number of moles of carbonate x to fall within the range of 0.092 to 0.5, insoluble matter in the color development processing tank is different from that of the conventional replenisher type. It has become possible to achieve stable processability without causing

In addition to the present invention as described above, the system for supplying the solid processing agent is changed from the above-mentioned hopper system to the seal packaging system or the solid packaging system which is divided and weighed in advance as shown in FIGS. It was also confirmed that, by further changing the solid processing agent from the powder form to the granule form and the tablet form, a more stable processability can be achieved.

Further, in the conventional replenishing solution system, when the replenishing rate is lowered, precipitates start to be generated in the replenishing solution and the processing stability is greatly lowered. Even if the amount of replenishing water decreases, it becomes possible to maintain stable processability, leading to reduction of chemical waste liquid.

Further, in the case of the seal packaging system and the system of FIGS. 10 and 11, when the unit supply amount of the solid color developing agent is less than 0.5 g, the number of times the solid processing agent is charged becomes abnormally high, and It was also confirmed that the replacement frequency was high and the workability was not good.

Example 2 Using the automatic processor described in Example 1, the color developing agent was changed to the exemplified compound (18), the unit supply amount of the solid color developing treatment agent, and the above y / x are shown in Table 6. The same solid color developer as in Example 1 was used except for the changes as shown, and 50 24 EXP color films per hour were continuously processed for 3 hours, and the number of prints (3750 E plates) was continuously run. .

After the above running experiment, the state of generation of insoluble matter in the color development processing tank was visually evaluated.
The results are shown in Tables 6 and 7.

[0198]

[Table 6]

[0199]

[Table 7]

As is apparent from Tables 6 and 7, the unit supply amount of the solid color developing treatment agent is set to 0.5 to 50 g, and the exemplary compound (1) contained in the solid color developing treatment agent is supplied in unit amounts. ) Ratio y / the number of moles x of carbonate salt y /
By setting x so as to fall within the range of 0.092 to 0.5, it became possible to prevent the generation of insoluble matter in the color development processing tank.

(Example 3) Konica Color Super DD-
After image-wise exposing 100 films, the color negative film processor CL-KP-50QA was modified in the same manner as in Example 1 and subjected to continuous processing.

The processing steps are shown below.

Processing step Processing time Processing temperature Color development 3 minutes 15 seconds 38.0 ° C Bleach 45 seconds 38.0 ° C Fixing-1 45 seconds 38.0 ° C Fixing-2 45 seconds 38.0 ° C Stability-1 20 seconds 38.0 ° C Stability-2 20 seconds 38.0 Stability -3 20 seconds 38.0 ℃ Dry 80 seconds 55 ℃ Fixing is from 2 to 1, stability is from 3 to 2,2 to 1 countercurrent method, and the bleaching tank is aerated with an air pump.

Evaporation correction is color development, bleaching, fixing-1, fixing-2, stable-1, stable-2, stable- during temperature control.
10ml, 6.5ml, 7ml, 7ml, 8.6ml in 1 hour each in 3 tanks
Evaporation correction was performed using a program that replenishes 8.6 and 9.3 ml of water. When not in operation, the non-operation time is added up, and color development, bleaching, fixing-1, fixing-2, stable-1, stable-2,
Stable -3 with evaporation-corrected water 7.5 ml, 5 m per hour each
The amounts of 1, 6 ml, 6 ml, 5 ml, 5 ml and 5 ml were collectively replenished with water at the start of operation. The tank solution at the start was prepared by using a replenisher solution of Konica Color Negative Film processing agent CNK-4-52 and a starter.

Next, the following color negative treating agent was prepared.

(1-1) Powder processing agent for color developing replenishment for color negative Exemplified compound of developing agent (3) Amount described in Table 9, hydroxylamine sulfate 69.4 g, 1-hydroxyethane 1,1-diphosphonate disodium 15 g, 72.8 g potassium sulfite, 350 g potassium carbonate, 3 g sodium hydrogen carbonate, sodium bromide
3.7g of each in a commercially available bandam mill, average particle size 10
It is pulverized to a size of μm, and these materials are uniformly mixed for 10 minutes using a mixer in a room where the humidity is controlled to 40% RH or less.
This was divided into unit amounts shown in Table 7 to prepare a powder processing agent (1) for color developing replenishment for color negative.

(1-2) Granular processing agent for color developing replenishment for color negative Operation (H) Exemplified compound of developing agent (3) Grind the amounts described in Tables 9 and 10 in a commercial Van Dam mill until the average particle size becomes 10 μm. . This fine powder is placed in a commercially available stirrer for about 7 minutes at room temperature for 10 minutes.
After granulating by adding ml of water, the granulated product is dried in a fluidized bed dryer at 40 ° C. for 2 hours to almost completely remove the water content of the granulated product, and color development replenishing granules for color negative (H) was prepared.

Operation (I) 69.4 g of hydroxylamine sulfate and 4 g of Pine Flow (manufactured by Matsutani Chemical Co., Ltd.) were pulverized in the same manner as in the operation (1), and then mixed and granulated. The amount of water added was 3.5 ml, and after granulation, it was dried at 60 ° C. for 30 minutes to almost completely remove the water content of the granulated product to prepare granules (I) for color development replenishment for color negative.

Operation (J) 1-Hydroxyethane-1,1-diphosphonate disodium 15
g, potassium sulphite 72.8 g, potassium carbonate 350 g, sodium hydrogen carbonate 3 g, sodium bromide 3.7 g and mannite 22 g are crushed and mixed in the same manner as in the operation (1), and the amount of water added is 40 ml for granulation. . After the granulation, the granulated product was dried at 70 ° C. for 60 minutes to almost completely remove the water content of the granulated product to prepare color development replenishing granules (J) for color negative.

The color developing replenishing granules (H) to (J) for color negative described above are mixed and divided by the unit supply amount shown in Tables 9 and 10, and the granules (2) for color developing replenishing for color negative are prepared.
And

(1-3) Tablet for color development replenishment for color negative operation (H ') Exemplified compound of developing agent (3) The amount described in Table 10 is pulverized in a commercially available bandam mill until the average particle size becomes 10 μm. This fine powder was granulated in a commercial stirred granulator at room temperature for about 7 minutes by adding 10 ml of water, and then the granulated material was dried in a fluidized bed dryer at 40 ° C. for 2 hours. The water content of the granulated product is almost completely removed. In this way, 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 with a mixer in a room where the humidity was adjusted to 25 ° C and 40% RH or less. Mix evenly for a minute. Next, the mixture is toughly pressed collect 152 made by Kikusui Seisakusho KK
A tableting machine modified from 7HU was used to perform compression tableting with an appropriate amount of the filling amount per tablet to prepare color development replenishing tablets (H ') for color negative.

Procedure (I ') 69.4 g of hydroxylamine sulfate and 4 g of Pine Flow (manufactured by Matsutani Chemical Co., Ltd.) were pulverized in the same manner as in the procedure (1), and then mixed and granulated. The amount of water added is 3.5 ml, and after granulation, it is dried at 60 ° C. for 30 minutes to almost completely remove the water content of the granulated product. In this way, 0.3 g of sodium N-lauroylalanine is added to the adjusted granulated product, and mixed for 3 minutes using a mixer in a room whose humidity is controlled to 25 ° C. and 40% RH or less. Further, in the same manner as in the operation (1), a tableting machine was used to compress and compress an appropriate amount of the filling amount per tablet to prepare a color negative color development replenishing tablet (I ′).

Procedure (J ') 1-hydroxyethane-1,1-diphosphonate disodium 15
g, potassium sulphite 72.8 g, potassium carbonate 350 g, sodium hydrogen carbonate 3 g, sodium bromide 3.7 g and mannite 22 g are crushed and mixed in the same manner as in the operation (1), and the amount of water added is 40 ml for granulation. . After the granulation, the granulated product is dried at 70 ° C. for 60 minutes to almost completely remove the water content of the granulated product. In this way, 2 g of sodium N-lauroylalanine is added to the adjusted granulated product, and mixed for 3 minutes using a mixer in a room whose humidity is controlled to 25 ° C. and 40% RH or less. Further, in the same manner as in the operation (1), a tableting machine was used to perform compression tableting by an appropriate amount of the filling amount of each tablet to prepare a color negative color development replenishing tablet (J ').

The above-mentioned appropriate amount means each tablet (H ') to
The weight ratio of (J ') was made equal to the total weight ratio of each granule, and the total amount of tablets (H') to (J ') was controlled to be the unit supply amount shown in Table 10.

The color developing replenishing tablets for color negative (H ') to (J') were combined to prepare a color developing replenishing tablet for color negative (3).

(1-4) Tablet for color development replenishment for color negative operation (H ″) Exemplified compound of developing agent (3) The amount described in Table 11 is ground in a commercial Van Dam mill until the average particle size becomes 10 μm. The powder was granulated in a commercial stirred granulator at room temperature for about 7 minutes by adding 10 ml of water, and then the granulated product was dried in a fluidized bed dryer at 40 ° C. for 2 hours to granulate. The water content of the product was almost completely removed to prepare granules (H ″) for color development replenishment for color negative.

Operation (I ″) 69.4 g of hydroxylamine sulfate and 4 g of Pineflow (manufactured by Matsutani Chemical Co., Ltd.) were pulverized in the same manner as in the operation (1), and then mixed and granulated. After granulation, the granules were dried at 60 ° C. for 30 minutes to almost completely remove water from the granules to prepare granules (I ″) for color development replenishment for color negative.

Procedure (J ″) 1-Hydroxyethane-1,1-diphosphonate disodium 15
g, potassium sulphite 72.8 g, potassium carbonate 350 g, sodium hydrogen carbonate 3 g, sodium bromide 3.7 g and mannite 22 g are crushed and mixed in the same manner as in the operation (1), and the amount of water added is 40 ml for granulation. . After the granulation, the granulated product was dried at 70 ° C. for 60 minutes to almost completely remove the water content of the granulated product to prepare a color developing replenishing granule for color negative (J ″).

The above-mentioned appropriate amount means each granule (H ″)
(J ″) is mixed in a proportion of each total weight, and the total amount of each of the granules (H ″) to (J ″) is controlled so as to be the unit supply amount shown in Table 11. 0.5
Add wt% sodium N-lauroyl alanine and add 3
After mixing for a minute, compression tableting was carried out using the above-mentioned tableting machine to obtain color developing replenishing tablet (4) for color negative.

2) Bleaching Replenishing Tablet for Color Negative Operation (K ') 1,3-Propanediaminetetraacetic acid Ammonium ferric monohydrate
175 g, 1,3-propanediamine tetraacetic acid 2 g and Pine Flow (manufactured by Matsutani Chemical Co., Ltd.) 17 g were pulverized and mixed in the same manner as in the operation (H), and the amount of water added was 8 ml to perform granulation. After the granulation, the granulated product is dried at 60 ° C for 30 minutes to almost completely remove the water content of the granulated product.

Operation (L ') 133 g of succinic acid, 200 g of ammonium bromide and pine flow
10.2 g is crushed, mixed and granulated in the same manner as in the operation (H). The amount of water added was 17 ml, and after granulation, the granules were dried for 60 minutes at 70 ° C to almost completely remove water.

Operation (M ') 66.7 g of potassium sulfate, 60 g of potassium hydrogen carbonate and 8 g of mannite are pulverized, mixed and granulated in the same manner as in the operation (H). The amount of water added is 13 ml, and after granulation, the granules are dried at 60 ° C for 60 minutes to almost completely remove water.

The granules prepared by the above operations (K ') to (M') are uniformly mixed for 10 minutes using a mixer in a room where the humidity is controlled to 25 ° C and 40% RH or less. Next, 6 g of sodium N-lauroyl sarcosine is added to this mixed granulated product, and they are mixed for 3 minutes. Next, the mixture was compressed into tablets using a tableting machine modified from Tough Pressed Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd. so that the filling amount per tablet was 6.5 g, and 80 bleaching supplement tablets for color negative were prepared. This was used as a color negative bleaching supplement tablet.

(3) Fixing replenishing tablet for color negative Ammonium thiosulfate 2500 g, sodium sulfite 150
g, 150 g of potassium carbonate, 20 g of ethylenediamine tetraacetic acid disodium salt and 65 g of Pine Flow (manufactured by Matsutani Chemical Co., Ltd.) are pulverized, mixed and granulated in the same manner as in the operation (1). How much water is added
After granulating to 50 ml, the granulated product is dried for 120 minutes at 60 ° C. to almost completely remove water from the granulated product.

[0225] The granulated product prepared by the above operation and 13 g of sodium N-lauroylsarcosine are mixed for 3 minutes with a mixer in a room where the humidity is adjusted to 25 ° C and 40% RH or less. Next, the mixture was compressed into tablets with a tableting machine modified from Tough Pressed Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd. so that the filling amount per tablet was 9.3 g, and 280 color fixing negative replenishing tablets were prepared. .

(4) Stable replenishing tablet for color negative m-hydroxybenzaldehyde 150 g, sodium lauryl sulfate 20 g, ethylenediamine tetrasodium acetate 60
g, 65 g of lithium hydroxide monohydrate and 10 g of pine flow are pulverized, mixed and granulated in the same manner as in the operation (H). How much water is added
After granulating to 10 ml, the granulated product is dried at 50 ° C. for 2 hours to almost completely remove the water content of the granulated product.

[0227] The granules prepared by the above operation are treated at 25 ° C and 40% RH.
Stable replenishment for 280 color negatives was performed in a humidity-controlled room with a tableting machine that was modified from Tough Pressto Correct 1527HU manufactured by Kikusui Seisakusho Co., Ltd., with a filling amount of 0.48 g per tablet. The tablets were made.

Using these solid processing agents, continuous running experiments were conducted in the same conventional replenisher system, hopper system, system of FIGS. 10 and 11 and seal packaging system as in Example 1, and color development after continuous processing was performed. The condition of the development processing tank and the transmission density of the highest color density portion were measured. The results are shown in Tables 9-11.

Table 8 shows the replenishment amounts in the bleaching, fixing and stabilizing steps.

[0230]

[Table 8]

[0231]

[Table 9]

[0232]

[Table 10]

[0233]

[Table 11]

As is clear from Tables 9 to 11, the unit supply amount of the solid color developing treatment agent is set to 0.5 to 50 g, and the exemplary compound (1) contained in the solid color developing treatment agent is supplied in unit amounts. ) Ratio y / the number of moles x of carbonate salt y /
By setting x so as to fall within the range of 0.092 to 0.5, it becomes possible to achieve stable processability without generating insoluble matter in the color development processing tank.

In addition to the present invention, the system for supplying the solid processing agent may be changed from the above-mentioned hopper system to the seal packaging system and the pre-divided and weighed system such as the systems shown in FIGS. It was also confirmed that, among them, even more stable processability can be achieved by changing the solid processing agent from powder to granules or tablets.

Further, in the case of the seal packaging system and the system of FIGS. 10 and 11, when the unit supply amount of the solid color developing agent is less than 0.5 g, the number of times the solid processing agent is charged becomes abnormally high, and It was also confirmed that the workability is not good because the replacement frequency of the will increase.

Exemplified compound (3) has higher water solubility than Exemplified compound (1) and can be highly concentrated without generating insoluble matter when strong stirring is performed. However,
When the solid color development processing agent is directly charged into the processing tank as in the present invention, the stirring property is not so strong and the solid color development processing agent is also contained in the unit supply amount and the unit supply amount thereof. It was confirmed that insoluble matter generation cannot be completely prevented unless both the ratio y / x of the number of moles y of the exemplified compound (3) and the number of moles x of the carbonate are set within the range of the present invention.

Further, in the conventional replenishing solution system, when the processing amount of the photosensitive material per day is small as in this embodiment, the exemplified compound (3) which is the color developing agent is easily oxidized in the replenishing solution tank, When the replenishment rate is further lowered, the oxidation of Exemplified Compound (3) becomes more violent and stable processability cannot be maintained. On the other hand, in the case of the present invention, even when the replenishment rate is lowered, the solid color developing treatment is performed. Stable processability can be maintained without causing poor dissolution of the agent, and reduction of the amount of chemical waste liquid is also achieved.

(Example 4) Using the automatic processor described in Example 3, the unit supply amount of the solid color developing agent and the above y / x were changed as shown in Tables 12 and 13 and Example 3. Using the same solid color developing agent, 24 EXP color film per hour
Fifty were continuously run for 3 hours.

[0240] After the running experiment, the appearance of insoluble matter in the color development processing tank was visually evaluated. The results are shown in Tables 12 and 13.

[0241]

[Table 12]

[0242]

[Table 13]

As is clear from Tables 12 and 13, the unit supply amount of the solid color developing treatment agent is set to 0.5 to 50 g, and the exemplary compound (1 ) Ratio y / the number of moles x of carbonate salt y /
By setting x so as to fall within the range of 0.092 to 0.5, it was possible to prevent the generation of insoluble matter in the color development processing tank.

Example 5 The same experiment as in Example 3 was conducted except that the color developing agent was changed to the exemplified compound (1).

As a result, as in Example 3, the unit supply amount of the solid color developing treatment agent was set to 0.5 to 50 g, and the exemplary compound (1) contained in the solid color developing treatment agent supplied in unit amounts. Ratio y / x of the number of moles of y and the number of moles of carbonate
By setting so that it falls within the range of 0.092 to 0.5,
It was confirmed that in the color development processing tank, stable processability was achieved without generating insoluble matter.

[0246]

EFFECTS OF THE INVENTION According to the present invention, firstly, it is possible to eliminate the liquid chemical that may pose a danger of transportation and handling, and to use the solid chemical without any complicated operation for the user. Completed a fully automated replenishment system by eliminating the dissolution work of the concentration kit by the user's own work. Third, it was made compact by eliminating many built-in refill tanks. Fourth, there was no need to store liquid replenisher. Achieve a low-pollution system with improved processing stability, reduced chemical waste, and fifthly, the use of plastic packaging materials without plastic bottles for liquids.
In addition, it is possible to supply a color developing solid processing agent for a silver halide photographic light-sensitive material, which achieves prevention of dissolution failure of the solid processing agent to be replenished and has greatly improved processing stability.

[Brief description of drawings]

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

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

FIG. 3 is a plan view of the automatic processor.

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

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

FIG. 6 is an apparatus showing a method of cutting off a package.

FIG. 7 is a perspective view of an apparatus showing the cutting method of FIG.

FIG. 8 is a perspective view of a powdery processing agent supply device.

FIG. 9 is a plan view showing a specific example of three-way seal and four-way seal packaging.

FIG. 10 is a sectional view of an automatic processor according to the present invention.

11A and 11B are a plan view and a side view of a storage container that stores a tablet-type solid processing agent.

[Explanation of symbols]

 1 Processing Tank 1A to 1E Processing Tank R Feeding Roller 2 Processing Section 3 Filter 4 Circulation Pipe 5 Circulation Pump 6 Drainage Pipe 7 Heater 8 Processing Quantity Information Detection Means 9 Processing Agent Supply Control Means 11 Solid Processing Agent Feeding Section 12 Partition Wall 13 Tablet 14 Filtering section (category) 15 Cartridge 16 Lead wire 17 Treatment agent supply means 17a Cutter 17b Opposing roller 23 Preliminarily programmed evaporative replenishment setting means 32 Hot water replenishing device 33 Solenoid valve 35 Drying section 36 Replenishment water supply 42 Means 43 Replenishment water tank 101 Treatment tank 102 Constant temperature bath 120 Solid treatment agent input unit 130 Solid treatment agent replenishing device 131 Treatment amount information detection means 132 Treatment amount supply control means 133 Storage container 331 Container body 332 Guide pin 333 Cap member 333B Identification protrusion (Loading prevention pin) 334 Slide lid J1A to J5A, J10A Tablet J1B Tablet J1C Tablet J1D Tablet

Claims (3)

[Claims] 1. Having at least one water-soluble group
A solid development agent for color development for silver halide photographic light-sensitive materials, which contains a p-phenylenediamine compound and a carbonate and is directly charged into the processing tank in the automatic developing machine in unit supply amounts (hereinafter, color development (Also referred to as a solid processing agent), the ratio y / x of the number of moles y of the p-phenylenediamine compound to the number x of carbonate salts in the unit solid-state developing agent for color development is 0.092 ≦ y / x. A color developing solid processing agent for a silver halide photographic light-sensitive material, characterized in that it is in the range of ≦ 0.5, and the unit supply amount of the solid developing agent for color developing is 0.5 to 50 g. 2. The silver halide photograph according to claim 1, wherein the solid developing agent for color developing for silver halide photographic light-sensitive material is granules formed by a granulation step or tablets formed by tableting. Color development solid processing agent for light-sensitive materials. 3. The color developing solid processing agent for a silver halide photographic light-sensitive material according to claim 2, wherein the color developing solid processing agent for a silver halide photographic light-sensitive material is divided and weighed in advance in a fixed amount. .