JPH06273894A - Solid processing agent package for silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve the stability and blocking property of solid processing agents and to improve the accuracy of replenishment by specifying the intra- package friction coefft. between the solid processing agents and the surfaces of packaging materials to a specific value or below. CONSTITUTION:The content of the alkali hydroxide metal compd. of the processing agents for silver halide photographic sensitive materials contg. the alkali hydroxide metal compd. is 0.05 to 0.5 by weight of carbonate. The solid processing agents 13 are dividedly weighed and partially packaged to a 0.5 to 50g per unit replenishing supply rate and the intra-package friction coefft. between the solid processing agents 13 and the surfaces of the packaging material is <=1.5. The solid processing agents 13 are granules or tablets rather than powder and further the moisture vapor transmission rate of the packaging materials is <=50g/m<2> 24hr. The packaging materials are partly unsealed by charging, rupturing, cutting and peeling by mechanical means, etc., and the solid processing agents 13 are transferred from the packaging materials into a processing tank 1 by gravity, etc., at the time of charging the solid processing agents 13 packaged by the packaging materials into the processing tank 1.

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 a silver halide photographic light-sensitive material, more specifically, the stability of the photographic processing agent is dramatically improved, replenishment accuracy is improved, and stable photographic performance is improved. The present invention relates to a solid processing agent package for a silver halide photographic light-sensitive material, which is provided, eliminates a melting operation, and can be made plastic bottle-free.

[0002]

2. Description of the Related Art Silver halide photographic light-sensitive materials are
Processing is performed by steps such as development, desilvering, washing and stabilization.
Processing is usually carried out by an automatic processor, in which case a replenisher replenishing system is generally widely used and is controlled so as to keep the activity of the processing solution in the processing tank constant. In the case of the replenisher replenishment method, the purpose is to dilute the eluate from the sensitive material, correct the evaporation amount, and replenish the consumption component.
A large amount of overflow liquid is usually discharged.

On the other hand, in recent years, there has been a worldwide increase in regulations regarding the dumping of photographic waste liquids into the ocean and regulations regarding the disposal of plastic materials. A new system that eliminates photographic waste liquids and does not use bottles for liquefaction processing agents Development is required. In addition, safety regulations for packaging materials have been strengthened to ensure the safety of transportation of liquid hazardous materials, which has led to an increase in cost. Also, at the minilab store, which has been increasing rapidly in recent years, part work is proceeding due to lack of manpower, it is difficult to dissolve or prepare the replenisher solution, and accidents due to erroneous dissolution occur one after another, causing many complaints about the replenishment system. It was

Therefore, in the photographic industry, there is a strong demand for the development of a solid chemical replenishing system which produces almost no photographic waste liquid, uses no processing agent bottle, and does not require any dissolving work.

As a method for responding to this demand, WO92-20013
In the official gazette, almost all processing components are made into solid processing agents,
A method of directly charging the treatment tank is disclosed. However, in this method, the solid processing agent is directly added to the processing tank, so that the processing agent adheres to the photosensitive material to be processed and causes an accident, or the evaporated water from the processing tank or the water in the atmosphere is absorbed, and The solid treatment agent may not be surely put into the treatment tank because the treatment agents stick to each other, or the solid treatment agent may be adhered to the packaging material to significantly reduce the feeding accuracy and the weighing accuracy. When an alkali metal hydroxide compound such as sodium hydroxide or potassium hydroxide is present in the solid processing agent, it tends to block with other solid processing agents regardless of the packaging state, and the weighing accuracy is greatly reduced. There was found. Further, the alkali metal hydroxide compound is partially dissolved,
There is also a problem during storage that it reacts with photographic components other than alkali metal hydroxide, for example, compounds such as sulfuric acid and hydrochloric acid that are salts of strong acids, causing discoloration of the solid processing agent and seriously affecting photographic performance. It was revealed.

Further, in Japanese Patent Laid-Open No. 4-237045, a method of setting powdery processing agents in a processing machine for each part, and weighing them into a processing tank while weighing each necessary amount, and a processing machine of this powder chemical A method for preventing moisture is disclosed. However, in this method, after the powder chemical is set on the automatic developing machine, the density changes due to its own weight, the predesigned amount of each part is not taken, the replenishment of the replenisher is not constant, and the photographic performance changes. It turns out that it will end up. Further, even if the evaporation water from the upper part of the processing tank is prevented to some extent, the problem of sticking due to moisture absorption of the solid processing agent at the inlet is unavoidable, and since the set powdery processing agent is left in the atmosphere, Accurate weighing cannot be achieved due to blocking of the powdery treatment agent and adhesion to the packaging material. As described above, the biggest drawback is that the amount of preparative change changes with the passage of time. See WO91
JP-A-7332 discloses a method in which a powder, granule or liquid processing agent is put into a pressure through package (PTP) packaging material and directly put into an automatic developing machine. However, this method merely technically discloses PTP packaging, and when alkali metal hydroxide compounds are present, blocking or adhesion with the packaging material occurs between solid processing agents regardless of the type of packaging material and replenishment. There is no mention that solid ingredients tend to remain in the packaging material and replenishment accuracy cannot be maintained.

The present inventors have examined a replenishing device and a packaging material for imparting moisture resistance to these problems.
I couldn't find a real solution. However, regarding the solid chemical containing the alkali metal hydroxide compound, which was the most difficult chemical for the above-mentioned problems, a specific amount of carbonate was present at the same time and it was packaged in one replenishing unit. If the static friction coefficient between the packaging material and the solid processing agent is less than a certain value, no blocking occurs even if stored for about 2 years at 80% relative humidity, and almost all the amount can be dropped by gravity. I found out.

The effect of the present invention relates to a solid processing agent used in a system for directly charging and replenishing a processing tank dissolving section in an automatic developing machine. In order to prevent the deterioration of replenishment accuracy due to blocking failure during adhesion between the packaging material and adhesion to the packaging material and the decrease in the components of the processing agent due to the chemical reaction in the packaging material due to the moisture absorption of the solid processing agent and the fluctuation of the photographic performance due to it. The alkali metal hydroxide and carbonate are allowed to coexist in the same packaging in a certain ratio, and the coefficient of friction between the solid processing agent and the surface of the packaging material is set to 1.5 or less to obtain a solid containing the alkali metal hydroxide. It has been found that the accuracy of addition and replenishment accuracy can be dramatically improved even if the chemical is stored for a long period of time.In the packaging form in which 0.5 to 50 g is dividedly weighed per replenishment unit supply amount. The one in which we found that stable photographic performance can be obtained.

[0009]

SUMMARY OF THE INVENTION The first object of the present invention is to:
It is to supply a solid processing agent package for a silver halide photographic light-sensitive material that eliminates the manual work of dissolving the concentration kit and enables an automatic replenishment system capable of highly accurate replenishment.

Second, eliminating the use of liquid plastic bottles,
It is to supply a solid processing agent package for silver halide photographic light-sensitive materials, which greatly reduces the use of plastic packaging materials and enables an environment-friendly low-pollution system.

Thirdly, it is to supply a solid processing agent package for a silver halide photographic light-sensitive material, which is free from liquid dangerous substances and is light in terms of physical distribution and safe.

Fourth, there is a supply of a solid processing agent package for a silver halide photographic light-sensitive material which makes it possible to drastically reduce the photographic processing waste liquid by dry replenishment with a solid chemical.

Fifth, it is to provide a replenishing system of the solid processing agent for silver halide photographic light-sensitive materials, which is remarkably improved in storage stability and weighing accuracy.

[0014]

SUMMARY OF THE INVENTION The above object is to provide a processing agent for a silver halide photographic light-sensitive material containing an alkali metal hydroxide compound in which the weight ratio of the alkali metal hydroxide compound to the carbonate is 0.05 to 0.5. A solid processing agent for a silver halide photographic light-sensitive material, wherein the solid processing agent is divided and weighed at 0.5 to 50 g per unit replenishment supply amount and packaged, and friction between the solid processing agent and the surface of the packaging material in the package. Achieved for the first time by a solid processing agent package for silver halide photographic light-sensitive material, characterized in that the coefficient is 1.5 or less, when the solid processing agent is granules or tablets rather than powder, further moisture permeability of the packaging material is 50 g. The effect of the present invention becomes more remarkable when it is / m ² · 24 hr or less.

[0015]

[Function] The inventors of the present invention have made the melting work and the bottle free,
It was proposed by Japanese Patent Application No. 4-301432, etc. that when solid processing agents are used for drastically reducing photographic waste liquid, it is preferable to pack and feed them in unit replenishment supply amount. Since solid treatment agents containing metal compounds have hygroscopicity and deliquescent, solid treatment agents stick to each other over time, blocking occurs, and they stick to the packaging material and remain in the package, which significantly improves loading accuracy and weighing accuracy. Lower,
Moreover, even if the moisture permeability of the packaging material is improved in order to suppress hygroscopicity, blocking still occurs due to changes in environmental conditions during manufacturing, transportation or presence, and changes in temperature and humidity in the packaging material. It is difficult to take out the agent when dropping it, let alone dropping it by its own weight,
The present inventors found out that it causes mechanical troubles, weighing, deterioration of input accuracy, and as a result has a serious influence on photographic performance, the present invention was completed by discovering the following experimental facts. It is a thing. In other words, the cause of solving various problems based on alkali metal hydroxide compounds is
Have discovered the fact that the presence of carbonate significantly suppresses the blocking formation due to the alkali metal hydroxide compound and the reaction with other components due to the partial dissolution of the alkali metal hydroxide compound. . Secondly, the above fact is that the effect of the carbonate is exerted only when the carbonate and the alkali metal hydroxide compound are present in the same package, both of which may or may not be granulated into the same particle, or Even if it is in the same tablet, it is packaged in the same sachet, and if the internal friction coefficient between the solid processing agent and the surface of the packaging material is 1.5 or less, it is effective, if it is a separate sachet, it is completely Thirdly, the effect of the carbonate is 0.005 to 0.5 in terms of the weight ratio of the alkali metal hydroxide compound to the carbonate.
When it is less than 0.5, the effect of the alkali metal hydroxide compound is little, and when it exceeds 0.5, the effect of the carbonate is almost lost. That is, when the solid processing agent packaged by the packaging material is put into the processing tank, a part of the packaging material is opened by opening, breaking, cutting, or peeling by a mechanical means, and the solid processing agent is dropped by its own weight or the like. Transfer from packaging material to processing tank. At that time, if the internal friction coefficient between the solid processing agent and the packaging material is maintained at 1.5 or less, the solid processing agent is smoothly charged into the processing tank, but if it exceeds 1.5, the packaging material is as described above. The solid processing agent remains inside, making it difficult to smoothly add it to the processing tank, causing an abnormality in the injection device, and the concentration of the processing agent component in the processing tank fluctuating due to a decrease in injection accuracy, resulting in large photographic characteristics. It fluctuates.

The above facts were clarified for the first time by a large amount of experiments by the present inventors and were quite surprising.

The present invention will be described in more detail below.

The solid processing agent of the present invention is a powder processing agent, a granular processing agent or a tablet, preferably a granular processing agent or a tablet from the viewpoint of charging accuracy. A powder is an aggregate of fine-grained crystals, and a granule has a particle size obtained by adding a granulation process to the powder.
It refers to particles of 50 to 5000 μm. A tablet refers to a powder or granules compression-molded into a certain shape.

A method for solidifying a photographic processing agent is disclosed in Japanese Patent Application No. 2-
No. 135887, No. 2-203165, No. 2-203166, No. 2-203167
No. 2-203168, No. 2-300409, etc. can be used.

As the granulation method for forming granules or tablets, known methods such as rolling granulation, extrusion granulation, compression granulation and fluidized bed granulation can be used, and the obtained granules are granulated. It is preferable from the viewpoint of input accuracy that 60% or more of the object particles fall within a deviation of ± 100 to 150 μm.

A method for producing a tablet processing agent is described in JP-A-51-61837.
No. 54-155038, No. 52-88025, British Patent 1,213,808
It can be produced by the specification such as No. and the like and a known method, and the granule treating agent is described in the specifications such as JP-A Nos. 2-109042, 2-109043, 3-39735 and 3-39739. Further, the powder processing agent, JP-A-54-133332, British Patent 725,892,
It can be produced by a known method as described in the specifications such as 729,862 and German Patent 3,733,861.

In the present invention, the solid processing agent contains at least an alkali metal hydroxide compound and a carbonate. Examples of the alkali metal hydroxide compound include lithium hydroxide, sodium hydroxide, potassium hydroxide and the like. Examples of the carbonate include sodium carbonate, potassium carbonate, ammonium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, and the like, and sodium carbonate and potassium carbonate are particularly effective in the present invention.

The weight ratio of the alkali metal hydroxide compound to the carbonate is 0.005 to 0.5. If it is less than 0.005, the effect of the alkali metal hydroxide is little, and if it exceeds 0.5, the effect of the carbonate is almost seen. Disappear.

The alkali metal hydroxide compound used in the present invention is 0.001 g to 0.2 g and the carbonate is 0.05 g to 0.90 g per 1 g of the solid processing agent. The term "per gram of the solid processing agent" as used herein means the total weight of the solid processing agent added per unit replenishment / supply amount converted into 1 g.

In addition to carbonates and alkali metal hydroxides, known photographic active ingredients, for example, color photographic ingredients include paraphenylenediamine color developing agents, hydroxylamine and its derivatives, black and white developers, and reduction of sulfites. Agent, fluorescent whitening agent, chelating agent, surfactant, organic acid ferric salt, alkali halide, buffer agent, antifungal agent, fixing component, etc., and can be used as a black and white developer. Examples thereof include derivatives thereof, methol, phenidone, and derivatives thereof, and the effect of the present invention becomes remarkable when they are preferably used in combination with a color developer component.

Particularly, when a color developing agent is present, it is a preferred embodiment in that the reaction between the color developing agent and the alkali metal hydroxide compound is suppressed and the photographic performance is maintained.

In the present invention, the solid processing agent is divided and weighed in 0.5 to 50 g per unit replenishment supply amount. The term "per unit replenishment / supply amount" refers to the total weight of the solid processing agent added when a certain amount of a silver halide photographic light-sensitive material is processed. If it is too much, dissolution failure of the solid processing agent is likely to occur, and if the unit supply amount is small, the number of times of charging for supplying a certain amount of the solid processing agent increases, and the accuracy of charging and the durability of the supplying means become a problem.

The packaging material of the present invention has an internal friction coefficient with the surface of the solid processing agent of the present invention of 1.5 or less, preferably
It is less than 1.0. Here, the coefficient of friction in the package is a value obtained by the following method.

The solid processing agent is put into the packaging material, and the packaging material is sealed and hermetically sealed. HEIDON's "Static Friction Tester HEIDON-1" was cut at both ends of the packaging material at a temperature of 25 ° C and a relative temperature of 40%.
0 "is used to fix the packaging material and measure tan θ at which 80% or more of the solid processing agent slips off the packaging material. This tan θ is the coefficient of friction within the package between the solid processing agent and the packaging material. The coefficient of friction in the package is the surface property, composition, size,
The coefficient of friction inside the package varies depending on the shape, the material of the packaging material, the surface roughness, and the state of storage, but the point is that the coefficient of friction inside the package between the solid processing agent and the packaging material reaches 1.5 or less when used. The object of the invention can be achieved.

Therefore, any packaging material may be used as long as the combination of the solid processing agent and the packaging material achieves an in-packaging friction coefficient of 1.5 or less. However, in the embodiment of the present invention, a synthetic resin material is used. Preferably used, specifically, polyethylene, polypropylene, polyvinyl chloride, polyvinyl acetate, nylon, polyvinylidene chloride, polystyrene, polycarbonate, vinylon, eval, polyethylene terephthalate and the like, even a single film or 2 It may be laminated with more than one kind of film, aluminum foil or the like may be used between the films, or a paper base coated with the above synthetic resin may be used.

The packaging material of the present invention has a coefficient of friction in the package with the surface of the solid processing agent of 1.5 or less, and a moisture permeability of 50 g / m ²
The effect of the present invention becomes more remarkable when the time is 24 hours (40 ° C./90% RH) or less. That is, when the water vapor permeability is high, the amount of water that passes through the packaging material increases, so that the solid processing agent that exhibits deliquescent partly deliquesces, causing an unfavorable reaction with other photographic components. This is because it also affects the friction coefficient. A packaging material having a moisture permeability of preferably 20 g / m ² · 24 hr or less is preferably used in the embodiment of the present invention.

The film thickness of the packaging material is 1 to 2000 μm from the viewpoints of usability, disposal of the packaging material, friction and moisture permeability.
More preferably, it is 10 to 1000 μm.

As a method for packaging the solid processing agent, there are four-sided seal, three-sided seal, stick (pillow packaging, gusset packaging), PTP (velister packaging), cartridge, etc., but the effect of the present invention is remarkably exhibited. Is a 4-way seal,
It is a three-way sticker and stick packaging. The four-sided seal, three-sided seal, and stick packaging are different in form, and the above materials are used. However, when the peel-open method is used, a sealant agent can be laminated to provide the peel-open suitability.

A method for supplying the solid processing agent to the processing tank is a method in which the solid processing agent, which is weighed and divided in a predetermined amount in advance, is added according to the processing amount of the photosensitive material, but the package is preferably opened. It is a method of taking out, a method of separating the adhesive surface when opening, a notch in a part of the seal packaging,
A method of opening by tearing, a method of cutting by an external force such as a cutter, and a method of forcibly pushing out the solid processing agent are preferably used.

The present invention will be described below in Examples.

[0036]

EXAMPLES The present invention will be described in detail below with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1 The following color development replenishing tablets for color paper were prepared.

Tablet- (1) 130 g of sodium p-toluenesulfonate, 3.5 g of sodium sulfite, 100 g of polyethylene glycol 6000, 60 g of mannitol and carbonate (shown in Table 1) are uniformly mixed with a commercially available mixer.

Next, this powder is granulated in a commercially available stirrer for about 20 minutes at room temperature. At this time, a solution prepared by dissolving an alkali metal hydroxide compound (shown in Table 1) in 50 g of water is used. Granulate while pouring. After the granulation, the granulated product is dried in a fluidized bed dryer at 60 ° C. for 1 hour to remove water almost completely. Next, 7 g of sodium N-lauroylalanine was added and mixed for 10 minutes, and the resulting mixture was mixed with a tableting machine modified from Tough Pressed Collect 1527HU manufactured by Kikusui Seisakusho Ltd.
The tablet was compressed to 1.85 g to prepare 200 tablets (1).

Next, using Tocello CMPSO11C as the sealant film of the tablet (1), the unstretched polypropylene film / stretched polypropylene film is laminated on the unstretched polypropylene film side (the solid processing agent is in contact with the unstretched polypropylene film). One tablet was packed in the peeled open package.

The packed tablets were placed in a constant temperature bath at 30 ° C and 80% RH.
It was put in for a month and the appearance and the coefficient of friction in the package were measured.

The results are shown in Table 1.

[0043]

[Table 1]

From the results shown in Table 1, when the alkali metal hydroxide compound is present, the friction coefficient in the package is increased, and particularly when the ratio of the alkali metal hydroxide compound to the carbonate exceeds 0.5, the measurement becomes impossible. Also, it can be seen that if it is less than 0.005, it hardly affects the friction coefficient in the package. On the other hand, the appearance also tends to be similar to the coefficient of friction in the package, and when it exceeds 0.5, some tablets are dissolved. From the above, when the weight ratio of the alkali metal hydroxide to the carbonate is 0.005 to 0.5, it is possible to suppress the partial friction and to keep the friction coefficient in the package low.

Example-2 In this example, an embodiment of the coefficient of friction in the package and the feeding accuracy is shown.

The samples used in Example-1 were packed in a series of 5 (FIG. 7 (D)), and whether or not they could be charged was observed using the solid processing agent charging device shown in FIG.

However, FIGS. 7D and 15 will be described later.

The results are shown in Table 2. Here, sample No. 27-
Although only 34 is described, the other samples show almost the same tendency.

[0049]

[Table 2]

As is clear from Table 2, there is a correlation between the coefficient of friction in the package and the feeding situation, and it can be seen that there is no problem if the coefficient of friction in the package is 1.5 or less. Samples No. 33 and 34, in which the ratio of potassium hydroxide to potassium carbonate exceeded 0.5, were not added.

Example 3 The following color development replenishing tablets for color paper were prepared.

Operation (A) The developing agent CD-3 [4-amino-3-methyl-N-ethyl-N-
[Β- (Methanesulfonamido) ethyl] aniline sulfate
300 g is ground in a commercial Van Dam mill to an average particle size of 10 μm. This fine powder was granulated in a commercial stirred granulator at room temperature for about 7 minutes by adding 50 ml of water, and then the granulated product was dried in a fluidized bed dryer at 40 ° C. for 2 hours. The water content of the granulated product is almost completely removed. In this way, 40 g of polyethylene glycol 6000 was added to the adjusted granules.
Mix evenly for 10 minutes using a mixer in a room where the temperature is controlled to ℃ and 40% RH or less. Next, 1 g of N-lauroylalanine sodium was added and mixed for 3 minutes, and the obtained mixture was manufactured by Kikusui Seisakusho Co., Ltd. Tough Pressed Collect 1527HU.
A tableting machine modified from No. 1 was used to perform compression tableting with a filling amount of 3.2 g per tablet, and 100 color developing replenishing tablets (A) for color paper were prepared.

Operation (B) Disulfoethylhydroxylamine disodium salt 120 g
Is pulverized and granulated in the same manner as in the operation (A). The amount of water added is 6.
After granulating to 0 ml, the granulated product is dried at 50 ° C. for 30 minutes to almost completely remove water from the granulated product. In this way, N-lauroylalanine sodium 4 was added to the prepared granules,
Mix for 3 minutes using a mixer in a room where the temperature is controlled to 40 ° C and 40% RH or less. Next, the mixture thus obtained was compressed into tablets using a tableting machine modified from Tough Pressed Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd., so that the filling amount per tablet was 1.0 g.
0 color development replenishing tablets (B) for color paper were prepared.

Procedure (C) Tinopearl SFP (manufactured by Ciba-Geigy) 30.0 g, sodium sulfite 3.7 g, potassium bromide 0.3 g, diethylenetriamine pentaacetic acid 25 g, sodium p-toluenesulfonate 280
g, 10.6 g of the alkali metal hydroxide compound shown in Table 3 and mannitol were pulverized in the same manner as in (A) and then uniformly mixed with a commercially available mixer. Next, in the same manner as in (A),
Granulate to 20 ml. After the granulation, the granulated product is dried at 60 ° C for 30 minutes to almost completely remove the water content of the granulated product. In this way, 4 g of sodium N-lauroylalanine was added to the prepared granules and mixed for 3 minutes using a mixer in a room whose humidity was adjusted to 25 ° C. and 40% RH or less. Next, the obtained mixture is manufactured by Kikusui Seisakusho Co., Ltd. Tough Press Collect 1527HU.
A tableting machine modified from No. 1 was used to perform compression tableting with the filling amount per tablet being 1.0 g, to prepare 100 color development replenishing tablets (C) for color paper.

Operation (D) The carbonates shown in Table 3 are pulverized and granulated in the same manner as in the operation (A). The amount of water added is 20 ml, and after granulation, the granules are dried for 30 minutes to remove water almost completely. In this way, polyethylene glycol 6000 was added to the adjusted granules.
Mix 15 g uniformly in a room controlled at 25 ° C. and 40% RH or less for 10 minutes using a mixer. Next, 4 g of sodium N-lauroylalanine was added and mixed for 3 minutes, and then the obtained mixture was manufactured by Kikusui Seisakusho Co., Ltd. Tough Pressed Collect 152.
Using a tablet machine modified from 7HU, the filling amount per tablet is 3.
Tablet compression was performed at 0 g to prepare 100 color development replenishing tablets (D) for color paper.

Each of the color paper color development replenishment replenishing tablets (A) to (D) was combined to obtain a color paper color development replenishment replenishment tablet (2).

The above-mentioned tablet (2) was packed in the same packaging as A, B, C and D in the same packaging material as in Example-1, and the evaluation contents and the hardness of the C agent of Example 1 were measured. . The hardness of the C agent was measured by using a speed checker TS-50N (Okada Seiko Co., Ltd.), and the tableting pressure was adjusted so that the hardness before being charged into the constant temperature tank was uniformly about 10 kg.

The results are shown in Table 3.

[0059]

[Table 3]

As is apparent from Table 3, the presence of the alkali metal hydroxide compound lowers the hardness, and the coefficient of friction in the package is abnormally high. Further, tablets A other than the self-tablet have black spots (tar). It turns out that it is easy to do. With this, it is sufficiently predicted that the powder will crush and accumulate powder during transportation or when a small amount of physical force is applied, which will seriously affect the loading accuracy and photographic performance. On the other hand, the alkali metal hydroxide compound is present in the same package as the carbonate and has a certain weight ratio (0.00
In the case of 5 to 0.5), the hardness of C tablet is high and the coefficient of friction in the package is also low due to the effect of carbonate, and it is found to be good.

Example 4 In this example, Samples 101 to 108 of Example 3 are used to show an embodiment of charging accuracy. Regarding the charging accuracy, the sample used in Example-3 was packaged in 5 packages (FIG. 7 (D)) and the solid processing agent charging device shown in FIG. The previous amount is shown as a percentage).

Note that FIG. 15 will be described later.

The results are shown in Table 4.

[0064]

[Table 4]

As is clear from Table 4, it is the sample of the present invention.
It can be seen that in all of 202 to 206, the C tablet was reliably put in and the weighing accuracy was good.

Example-5 The following granules for color development replenishment for color paper were prepared.

Operation (A) CD-3 [4-amino-3-methyl-N-ethyl-N-, a developing agent
[Β- (Methanesulfonamido) ethyl] aniline sulfate
300 g is ground in a commercial Van Dam mill to an average particle size of 10 μm. This fine powder was granulated in a commercial stirred granulator at room temperature for about 7 minutes by adding 50 ml of water, and then the granulated product was dried in a fluidized bed dryer at 40 ° C. for 2 hours. The water content of the granulated product was almost completely removed to prepare a granule processing agent (A) for replenishing color paper color development.

Operation (B) Disulfoethylhydroxylamine disodium salt 120 g
Is pulverized and granulated in the same manner as in the operation (A). The amount of water added is 6.
After granulating to 0 ml, the granulated product 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 replenishing color paper color development.

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 280
g, 10.6 g of an alkali metal hydroxide compound shown in Table 5 and mannitol are pulverized in the same manner as in (A), and then uniformly mixed with a commercially available mixer. Next, in the same manner as in (A),
Granulate to 20 ml. 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 paper color development replenishment.

Operation (D) The carbonates shown in Table 5 are pulverized and granulated in the same manner as in the operation (A). The amount of water added was 20 ml, and after granulation, the granulated product was dried for 30 minutes at 70 ° C. to almost completely remove the water content to prepare a granule processing agent (D) for color development replenishment for color paper.

The above color paper color development granule processing agents (A) to (D) were mixed and divided into 150 equal parts to obtain 150 color paper color development development replenishment granule processing agents (3).

Using the above-mentioned granule treating agent (3) as a sealant film, Tocello CMPSO11C was laminated on the unstretched polypropylene film / non-stretched polypropylene film surface of a high-density polyethylene film, and packaged in a four-sided sealed package by heat welding. . Packaged tablets at 30 ℃
The sample was placed in an 80% RH thermostat for one month, and the appearance, the coefficient of friction in the package, and the residual amount of the solid processing agent were measured. The residual amount of the solid processing agent was measured by using the solid processing agent supply device shown in FIG. 15 in which the sachets were packaged in five, and the residual amount relative to the weight before addition was also measured, and expressed as a percentage.

The results are shown in Table 5.

[0074]

[Table 5]

As is clear from Table 5, even in the case of the granule treating agent, the friction coefficient in the package becomes high due to the presence of the alkali metal hydroxide compound, and the residual rate of the solid treating agent becomes high. There is a concern that the width will decrease and the processability will be affected. CD that appears to be dissolved or tar in some of the granules
There is a discoloration of -3. On the other hand, it can be seen that the above problem is greatly improved by coexisting carbonate.

Example 6 CD-3 [4-amino-3-methyl-N-ethyl-N-, a developing agent
[Β- (Methanesulfone and) ethyl] anilan sulphate]
300 g, disulfoethylhydroxylamine disodium salt 120 g, Chinopearl SFP (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, potassium carbonate 350 g are crushed in a commercially available bandam mill to an average particle size of 10 μm, and these materials are homogenized for 10 minutes using a mixer in a room where the humidity is controlled to 40% RH or less. And mix this into 100 equal parts to give 100
A powder processing agent (4) for replenishing color development for color paper was prepared.

When the above powder treatment agent was evaluated in the same manner as the granule treatment agent of Example 5, almost the same effect could be obtained, but the solid treatment agent remaining in the packaging material was higher than that of the granule treatment agent.
Nearly 50% more.

Example 7 The following color negative treating agent was prepared.

(1) Powder processing agent for color development replenishment for color negatives Developing agent CD-4 [4-amino-3-methyl-N-ethyl-β- (hydroxy) ethylaniline sulfate] 150 g, hydroxylamine sulfate 69.4 g , 1-hydroxyethane 1,1-diphosphonate disodium 15g, potassium sulfite 72.8g, potassium carbonate
375 g, 3 g of sodium hydroxide, and 3.7 g of sodium bromide were crushed in a commercially available bandam mill to an average particle size of 10 μm, and these materials were mixed with a mixer in a room where the humidity was controlled to 40% RH or less. The mixture was uniformly mixed for 1 minute, and this was divided into 120 equal parts to prepare 120 pieces of powder processing agent (1) for replenishing color developing for color negative.

(2) Granule processing agent for color development replenishment for color negative operation (H) Developing agent CD-4 [4-amino-3-methyl-N-ethyl-β-
150 g of (hydroxy) ethylaniline sulfate] are pulverized in a commercially available bandam 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.

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 (H), 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.

Procedure (J) 1-Hydroxyethane-1,1-diphosphonate disodium 15
g, potassium sulphite 72.8g, potassium carbonate 375g, sodium hydroxide 3g, sodium bromide 3.7g and mannite 22g are crushed and mixed in the same manner as in step (H), 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.

Granules (H) to (J) for color development replenishment for color negative described above were mixed and divided into 120 equal parts to obtain 120 granules for color development replenishment for color negative (2).

(3) Color development replenishing tablet operation for color negative (H ') Developing agent CD-4 [4-amino-3-methyl-N-ethyl-β-
(Hydroxy) ethylaniline sulfate] 150 g is pulverized in a commercially available bandam mill until the average particle size becomes 10 μm. 10 ml of this fine powder in a commercial stirred granulator at room temperature for about 7 minutes
After granulating by adding 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. In this way, N-lauroylalanine sodium 0.3 g and polyethylene glycol 6000 1.9 g were added to the adjusted granules, and the mixture was mixed with a mixer in a room where the temperature was adjusted to 25 ° C and 40% RH or less. Mix evenly for a minute. Next, the mixture was made into a tough pressed collect 1527 manufactured by Kikusui Seisakusho KK
Filling amount per tablet is 1.1g with a tablet machine modified from HU.
Then, compression tableting was carried out to prepare 120 color developing replenishing tablets (H ') for color negative.

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 (H'), and then mixed,
Granulate. The amount of water added is 3.5 ml, and after granulation, 30 at 60 ℃
Dry for a minute to almost completely remove the water content of the granulated product. In this way, 0.3 g of sodium N-lauroylalanine is added to the adjusted granulated product, and mixed for 3 minutes using a mixer in a room where the humidity is adjusted to 25 ° C. and 40% RH or less. Further, in the same manner as in the operation (H '), compression tableting was carried out with a tableting machine at a filling amount of 0.56 g per tablet to prepare 120 color development replenishing tablets (I') for color negative. did.

Procedure (J ') 1-hydroxyethane-1,1-diphosphonate disodium 15
g, potassium sulphite 72.8g, potassium carbonate 375g, sodium hydroxide 3g, sodium bromide 3.7g and mannite 22g are crushed and mixed in the same manner as in the operation (H '), and the amount of water added is 40 ml for granulation. To do.

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 prepared 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 (H '), a tableting machine was used to perform compression tableting with the filling amount per tablet being 3.9 g to prepare 120 color development replenishing tablets (J') for color negative. did.

The above tablets (H ') to (J') were combined one by one to give a color developing replenishing tablet (3) for color negative.

The above-described powder processing agent for color negative, processing agent for granules and tablet were evaluated in the same manner as in Examples 1 to 6, but almost the same effects could be obtained.

Further, a developing agent for color negative CD-4 [4-amino
-3-methyl-N-ethyl-β- (hydroxy) ethylaniline sulfate] to CD-3 [4-amino-3-methyl-N-ethyl-N- [β-
(Methanesulfonamido) ethyl] aniline sulphate] and [4-amino-3-methyl-N-ethyl-β- (hydroxy) propylaniline sulphate], the occurrence of tar (less discoloration) The result was improved.

Example 8 In Sample 5 of Example 1, the unstretched polypropylene film / stretched polypropylene film was replaced with the packaging material shown in Table 6, and the coefficient of friction in the package, the residual rate of the solid processing agent and the hardness were measured. The results are shown in Table 6.

[0092]

[Table 6]

As is clear from Table 6, even with the solid treating agent of the present invention, when the friction coefficient in the package exceeds 1.5, the residual rate of the solid treating agent is high and the weighing accuracy is drastically reduced. However, there are problems such as partial dissolution and large breakage of the shape, but it is understood that there is no particular problem as long as it is the coefficient of friction in the package within the present invention. Especially, the coefficient of friction in the package is 1.0 or less.

Example-9 Using the sample No. 305 of Example 5, the same evaluation (removal hardness) as in Example 8 was performed.

The results are shown in Table 7.

[0096]

[Table 7]

As is clear from Table 7, even in the case of the granule treating agent, the residual rate of the solid treating agent is low when the coefficient of friction in the package is 1.5 or less, as in the case of the tablet, and particularly when it is 1.0 or less, the effect is large.

Example 10 Example 3 Using Sample 105, the packing material was changed to an unstretched polypropylene film / high density polyethylene film, and a material having moisture permeability shown in Table 8 was used.
θ) and the residual rate of the solid processing agent were measured.

The results are shown in Table 8.

[0100]

[Table 8]

As is clear from Table 8, when the moisture permeability is small, the coefficient of friction in the package is low and the residual rate of the solid processing agent is also small. Therefore, it is preferable that the moisture permeability is small in the embodiment of the present invention. I understand.

Example-11 Next, a packaging form used in the present invention will be described.

FIGS. 1A, 1B and 1C are plan views showing examples of four-way seals. FIG. 1D shows an example of a three-way seal. 2A and 2B show specific examples of stick packaging, but are not limited to these.

FIG. 3 shows a specific example of PTP packaging. However, it is not limited to these. FIG. 3 (A) shows a solid treatment agent in the form of a pill packed in PTP, and FIG. 3 (B) shows a state in which a plurality of tablets of the treatment agent are packaged.
FIG. 3C shows a state in which tablets, granules, or powders are contained in a column. FIG. 3 (D) shows these packages connected in one horizontal row. Alternatively, it may be a blister-like one as shown in FIG.

FIG. 4 shows a specific example of collective packaging. However, it is not limited to these. FIG. 4 (A) shows that the solid processing agent is contained in a cylindrical container, and FIG. 4 (B) shows that the solid processing agent is stored in a flexible two-side sealed or three-way sealed bag.
FIG. 4C shows a bag in which the solid processing agent is housed and one side of which is sealed.

5 and 6 are perspective views showing a specific example of the cartridge.

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

FIG. 5 (A) shows a tablet containing a tablet in a cylindrical cartridge, and FIG. 5 (B) shows a tablet containing granules or powder.

FIGS. 5C and 5D are a perspective view and a sectional view showing a mode in which a solid processing agent is contained in a box-shaped cartridge having an opening / closing lid.

FIG. 6 shows that tablets, granules or powders are contained in a rotatable container having a partition wall and further contained in an outer cylinder (main body), and a predetermined amount is dropped from the opening. FIG. 6 (A) shows a type in which the rotary shaft is horizontally supported,
FIG. 6B shows a type in which the rotary shaft is vertically supported.

The present invention is not limited to these specific examples.

The three-way seal or the four-way seal is superior in manufacturing cost, wrapping property and versatility, and requires less waste, and the effect of the present invention is remarkably exhibited.

Example-12 Next, the form of packing will be described by taking a preferable seal packaging for carrying out the present invention as an example.

In FIG. 7A, several kinds of tablets are contained in one packaging unit. For example, in the case of a color development replenishing tablet, a tablet formed for each of the alkali part, the main drug part, and the preservative part is contained in one packet as one supply unit. In (B), tablets of different types and sizes are individually packaged. For example, in the case of color development replenishing tablets, an alkaline part, a main drug part, and a preservative part are individually packaged,
A, B and C make up one set of supply units. (C) is a package of granules or powder. In this case, 1 packet is 1
One supply unit. (D) is an example in which the same size is contained, but in this case, one supply unit may be packaged in one sachet, or one supply unit in several sachets. (E) contains a plurality of same chemicals of the same size. (F) to (H) are examples in which granules are packaged in each part, and (P) are those in which they are separated in each package. (I) to (O) and (Q) to (X) show other examples of packaging of tablets.

In the present invention, the effect is exhibited only when the alkali metal hydroxide compound and the carbonate are present in the same package. Further, as an embodiment of the present invention, it is preferable that one supply unit is one-minute packaging, which has a favorable effect on loading accuracy and weighing accuracy, and has a merit that cost can be reduced.

Example-13 Specific examples of the automatic processor and the charging device used in the present invention will be described.

An example of an automatic developing machine (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. 8 is a schematic diagram of a printer processor in which the automatic developing machine A and the photo printing machine B are integrally configured.

In FIG. 8, 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.

Needless to say, the automatic developing machine according to the present invention may be constructed integrally with the photo printing machine B or may be a single automatic developing machine. Further, it goes without saying that the silver halide photographic light-sensitive material processed by the automatic developing machine according to the present invention is not limited to exposed photographic paper, and may be exposed negative film or the like. Further, the description of the present invention will be made on a developing machine of substantially three tanks including a color developing tank, a bleach-fixing tank, and a stabilizing tank, but the present invention is not limited to this, and the color developing tank, the bleaching tank, and the fixing tank can be used. The present invention can be applied to an automatic developing machine having substantially four tanks including a tank and a stabilizing tank.

FIG. 9 is a schematic view of a color developing tank 1A which is a processing tank in the I-I cross section of the automatic developing machine A of FIG. The bleach-fixing tank 1B and the stabilizing tanks 1C, 1D, and 1E have the same configuration as the color developing tank 1A. Therefore, when the processing tank 1 is described below, the color developing tank 1A, the bleach-fixing tank 1B, and the stable tank are stable. All of the tanks 1C, 1D and 1E will be referred to. It should be noted that, in the figure, a transporting means for transporting the photosensitive material and the like are omitted for easy understanding of the configuration. Further, in this example, the case where the tablet 13 is used as the solid processing agent will be described.

The processing tank 1 is a processing section 2 for processing a photosensitive material.
And a solid processing agent feeding section 11 for supplying tablets 13 integrally provided on the outside of the partition wall forming the processing section. The processing section 2 and the solid processing agent feeding section 11 are partitioned by a partition wall 12 having a communication window formed therein, so that the processing liquid can flow. Since the input section 11 is provided with a filtering section (section) 14 for receiving the treating agent, the treating section 2 remains solid.
Never move to.

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

The circulation system is composed of a circulation pipe 4 forming a liquid circulation passage, a circulation pump 5, a treatment tank 1 and the like. The other end of the circulation pipe 4 communicating with the discharge side of the circulation pump 5 penetrates 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. 9, and may be the opposite direction.

The waste liquid pipe 6 is for overflowing the processing liquid in the processing section 2, and keeps the liquid surface level constant, as well as components brought into the photosensitive material from other processing tanks and the photosensitive material. The component leaching from the material is stored,
Helps prevent the increase.

The rod-shaped heater 7 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 printer capable of indirectly detecting the processed area of the photosensitive material, for example, in the case of a printer processor as shown in FIG. 8, the amount of the photosensitive material subjected to printing, 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, but it is preferable to provide one for each automatic developing machine.

The treating agent supplying means 17 for introducing the solid treating agent accommodated in the package accommodating box (cartridge) 15 as the accommodating means into the treating tank is arranged above the filtering section (section) 14.

The tablets 13 stored in the cartridge 15 are shown in FIG.
Tablets individually packaged by the seal package shown in Fig. 1 and ejected from the cartridge 15 by the transport roller 17b.
The 13-containing seal package 16 is cut by the cutter 17a. The gravitational force causes the tablets 13 to be loaded into the filtering section (section) 14 from the opened seal package.

The processing agent supply means 17 is controlled by the processing agent supply control means 9 which will be described later, and in association with the supply signal issued from the processing agent supply control means 9, the tablets 13 are placed in the solid processing agent input section 11. It is supplied to the filtering section (section) 14. In addition,
In the present invention, the solid processing agent 13 is supplied to the filtering section (section) 14 in the solid processing agent input section 11, but the location to be supplied may be supplied to any location in the processing tank 1, that is, the present application. In the invention, it is only necessary that the solid processing agent can be dissolved using the processing liquid,
The components according to the processing amount information of the photosensitive material are surely added,
It is necessary to keep the processing characteristics of the processing liquid in the processing tank 1 constant, but more preferably, the solid processing agent is preferably supplied in the circulation path of the processing liquid. In addition, the treatment agent supply means 17 is configured so that moisture in the treatment tank of the automatic processing machine and humidity in the outside air, and scattered treatment liquid do not come into contact with the solid treatment agent before being supplied to the treatment tank. Is preferred.

The filtering 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 parts, etc. is there.

The filter section (section) 14 is preferably 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 supply means 17 are the photosensitive material conveying path shown in FIG. 8 or the processing section. It may be added to the treatment liquid in No. 2.

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

The replenishment water supply means 42 is means for replenishing replenishment water (replenishment water) from the replenishment water tank 43 for storing replenishment water to the treatment agent input part 11, and is a hot water replenishing device including a pump, a temperature controller, an electromagnetic It has a valve and a rehydration pipe. This replenishing water supply means 42
Is for compensating the water taken out by the photographic material and the water evaporated from the surface of the tank, while diluting the cumulative inhibitory component eluted by the reaction. Reference numeral 23 in the figure denotes evaporative replenishment water setting means.

FIG. 10 is a schematic top view showing the automatic developing machine A of FIG. 8 from above (however, the route is described for the rehydration means for explanation). 42 is a replenishment water supply means, 33 is a solenoid valve, and 36 is a replenishment pipe.

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

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

Next, the operation of the present invention will be described with reference to FIG. The processed amount information of the exposed photosensitive material is detected by the processed amount information detecting means 8 at the entrance of the automatic developing machine A. The processing agent supply control means 9 supplies a processing signal to the processing agent supply means 17 when the cumulative area of the photosensitive material to be processed reaches a predetermined area in accordance with the processing amount information detected by the processing amount information detecting means 8. Emit. Upon receiving the supply signal, the processing agent supply means 17 uses the conveying roller 17b to cut the tablet 13-containing three-way sealed package carried from the cartridge 15 by the cutter 17a.
The tablets 13 are cut, and the tablets 13 are supplied to the filtering section (section) 14 in the solid processing agent feeding section 11 by gravity. The supplied tablets 13 are dissolved by the processing liquid in the solid processing agent feeding section 11, but by the circulation means, the solid processing agent feeding section 11 → circulation pump 5 → processing section 2 → communication window → solid processing agent feeding section 11 Dissolution is promoted by the circulating processing solution.

Simultaneously with the above operation, the replenishment water supply means 42 receives the signal from the replenishment water quantity setting means 23, and the replenishment water is supplied to the treatment tank.

On the other hand, the detected light-sensitive material is successively conveyed by the roller conveying means in the color developing tank 1A, the bleach-fixing tank 1B and the stabilizing tanks 1C, 1D and 1E (see the automatic developing machine A in FIG. 8).

The color developing tank 1A, which is a processing tank,
Bleach-fixing tank 1B, stabilizing tanks 1C, 1D, 1E,
The processing agent supply means 17 may be provided and may be supplied simultaneously. Further, the timings supplied by the respective supply means may be different from each other, and further, the predetermined area for controlling the processing agent supply means by the processing agent supply control means 9 has a predetermined area. , 1C, 1D, 1E may be the same, but it goes without saying that they may be different from each other.

Further, FIGS. 11A and 11B and FIGS. 12A and 12B
Another embodiment of FIGS. 13 and 14 will be described.

FIGS. 11 (a) and 11 (b) show a "U-shaped" half punching system.

When the photosensitive material is processed, it is detected by the processing amount information detecting means 8, and when a certain amount is reached, a signal is sent by the processing agent supply control means 9 to rotate the conveying roller 17b, and the solid processing agent. The package 16 containing 13 is moved to the position shown in FIG. 11 (a) and stopped. The method of moving the package 16 includes a method of detecting a notch provided in the package 16 in advance, a print pattern or an eye mark, and a treatment agent 13 for the package 16.
Any method such as the detection of
It is enough to detect 10 with high accuracy. Next, as shown in FIG. 11 (b), the punch male mold 300 moves downward to cut the packaging body 16 and the solid processing agent 1
3 is put into the processing tank of the automatic developing machine through the filtering section (section) 14 of FIG. 12 (a). The cut end cut by the punch male die 300 has a U-shape like a punch shape 601 as shown in FIG.

In the case of such a system, the solid processing agent 13 may be any of powder, granules and tablets, but it is preferable to use the punch male type tablet which is hard to be attached with chemicals. Further, the tablets 13 do not adhere to the package so much that stains are less likely to occur, and are safe for the user to handle. Used packaging 16 is waste box 10
It can be put together in 2 and discarded. This waste bin 102
It is preferable to reuse the used package storage box 15.

13 and 14 show a method of cutting off the package 16.

When the photosensitive material is processed, it is detected by the processing amount information detecting means 8, and when a certain amount is reached, a signal is sent by the processing agent supply control means 9 to rotate the conveying roller 17b, and the solid processing agent. The package 16 containing 13 is treated with the solid treatment agent 13
Is moved to the position above the filtering section (section) 14 and stopped. At this time, the tip of the package 16 is in the ironing roller 17C.

Next, the ceramic cutter 17a is attached to the package 11.
Disconnect. When the cutting is completed, the ironing roller 401 and the conveying roller 17b rotate, and the solid processing agent 13 irons the ironing roller 17C.
Then, it is squeezed, passes through the discharge port, and is put into the filter section (section) 14 of the automatic developing machine. The cut waste package is discharged by the transport roller 17b and enters the waste box 102. This waste box 1
For 02, it is preferable to reuse the used package storage box 15.

In the case of such a system, the solid processing agent 13 may be any of powder, granules and tablets, but it is preferable to use tablets in which chemicals do not adhere to the ceramic cutter 17a. Further, the tablets have an advantage that they do not adhere to the package 16 so much that stains are less likely to occur.

The used packaging body 16 can be put together in the waste box 102 and discarded.

In FIG. 15, the storage box 15 stores the treatment agent package 16 in a state where the band portion is meandering. The tip of the treatment agent package 16 has rollers 8-a and rollers 8-b. Is fed by a first conveying means 8A composed of a drive means and driving means, or is opened and guided by a lid 7A, and is passed over a roller 9-a, a second conveying means 9A composed of a roller 9-b and a driving means, and a lid. By closing 7A, the first conveying means 8A and the second conveying means 9A are engaged. Before engaging with the second conveying means 9A, the cutting means (cutter) 10A separates the upper and lower seal portions and guides them in the direction of arrow A to eliminate them.

The above is one example of the treating agent supplying means used in the present invention, but the present invention is not limited to these, and the solid treating agent of the present invention is stably supplied onto the treating tank. Any method may be used as long as it is a means, but in order to achieve the effect of the present invention, a method of removing the laminating portion by the cutting and opening means shown in FIGS.

Next, FIG. 16 will be described.

A cylindrical solid processing agent package 130 accommodating a tablet type solid processing agent 13 is provided, and the processing agents 13 are stacked in a flat shape so that the tray 130 is lowered by its own weight when the shutter is opened. It can be supplied to and transported from here. This solid processing agent package is polyethylene-coated on the outside / inside,
The inside is made of paper.

A rotary shutter disk concentric with a support shaft 141 provided at a position spaced apart from the center of the solid processing agent package 130 by a certain distance so as to form the bottom of the solid processing agent package 130. 144 and fixed disk at the bottom in contact with it 1
42 are provided, and windows 145 and 143 are separately formed in each disk on the same concentric circle as the solid processing agent package 130.

The window 145 of the rotary shutter disk 144 has an inner diameter equal to or slightly larger than the inner diameter of the solid processing agent package 130 and the tablet type solid processing agent outer diameter dimension.

At the position where the rotary shutter disk 144 rotates and the window 145 overlaps so as to be concentric with the solid processing agent package 130, the lowermost solid processing agent 13 in the package 130 is placed in the window 145.
The rotary shutter disc 144 is further rotated and the window 143 of the fixed disc 142 and the window 145 are concentrically overlapped with each other. The solid processing agent 13 is dropped onto the window 143, and the shooter 146 is placed on the surface of the processing liquid of the filtering section 14 placed therebelow.
Is supplied by sliding down.

Example-14 Using the automatic processor shown in FIGS. 8 and 9, continuous processing was carried out in the processing steps shown below.

Konica QA Paper Type A-5 (Konica Corp.) was used as the treated color paper.

Processing step Processing time Processing temperature Color development 22 seconds 38.5 ° C Bleach fixing 22 seconds 38.0 ° C Stable-1 22 seconds 35-38 ° C Stable-2 22 seconds 35-38 ° C Stable-3 22 seconds 35-38 ° C Dry Stable for 50 seconds was a countercurrent system from 3 to 1, and all the overflow solution of stable-1 was flown into the bleach-fixing tank. The carryover per 1 m ^{2 of} light-sensitive material is 20 ml / in all tanks.
It was m ² .

Evaporation correction is carried out at the time of temperature control at color development, bleach-fixing, and stability of 9.0 ml / hour, 7.2 ml / hour, and 14.1 ml / hour for each 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.

Konica color Q is used as the starting tank liquid.
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 28
It was created using P-3B (same as above).

Next, the following color paper treating agent was prepared.

(Color development replenishing tablet for color paper)
Using the color development replenishing tablet for color paper of Example 3. However, in the operation (C), 20 g of potassium hydroxide was used as the alkali metal hydroxide compound, and in the operation (D), 350 g of potassium carbonate was used as the carbonate, and a color development replenishing tablet for color paper was used.

However, the compression amount was carried out by adjusting the filling amount per tablet to an appropriate amount shown in Table 4. The appropriate amount is tablets (A)
The total amount of (D) to (D) was controlled so as to be the unit supply amount shown in Tables 1 and 2.

(Bleach-fixing replenishing tablet for color paper) Operation (E) Diethylenetriamine pentaacetic acid ferric ammonium monohydrate
1250g, ethylenediaminetetraacetic acid 25g, maleic acid 250g,
Pine Flow (Matsuya Chemical Co., Ltd.) 46 g is pulverized, mixed and granulated in the same manner as in the operation (C). The amount of water added was 80 ml, and after granulation,
The granules are dried at 60 ° C. for 2 hours to almost completely remove water. In this way, 15 g of sodium N-lauroylsarcosine is added to the prepared granules, and they are mixed for 3 minutes by using a mixer in a room whose humidity is adjusted to 25 ° C. and 40% RH or less. Next, the resulting mixture was compressed into tablets with a tableting machine modified from Tough Pressto Correct 1527HU manufactured by Kikusui Seisakusho Co., Ltd. with a filling amount of 8.6 g per tablet, and bleach-fixing replenishment for 170 color papers. Tablet A for tablets was prepared.

Operation (F) 1640 g of ammonium thiosulfate, 750 g of sodium sulfite,
40 g of potassium bromide and 50 g of p-toluenesulfinic acid are pulverized, mixed and granulated in the same manner as in the operation (C). The amount of water sprayed is 10
After granulating to 0 ml, the granulated product is dried at 60 ° C. for 120 minutes to almost completely remove water from the granulated product. In this way, 20 g of sodium N-lauroylsarcosine was added to the adjusted granules,
Use a mixer in a room where the temperature is controlled to 5 ° C and 40% RH or less 3
Mix for minutes. Next, the resulting mixture was compressed into tablets using a tableting machine modified from Tough Pressed Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd., so that the filling amount per tablet was 13.4 g, and 170
A bleach-fixing replenishing tablet B agent for color paper was prepared.

Each of the bleach-fixing replenishing tablets for color paper (E) and (F) was combined to prepare a bleach-fixing replenishing tablet for color paper.

(Stable supplement tablet for color paper) Sodium carbonate monohydrate 10 g, 1-hydroxyethane-1,1-diphosphonate disodium 200 g, Tinopearl SFP 150 g, sodium sulfite 300 g, zinc sulfate heptahydrate 20 g, ethylenediamine Tetraacetic acid disodium 150g, ammonium sulfate 200
In the same manner as in the operation (C), g, 10 g of o-phenylphenol and 25 g of pine flow are pulverized, mixed and granulated.

The amount of water added was 60 ml, and after granulation, 60 ° C. at 60 ° C.
Dry for a minute to almost completely remove the water content of the granulated product. In this way, 10 g of N-lauroyl sarcosine sodium is added to the prepared 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. Next, the obtained mixture was toughly pressed collect 1527HU manufactured by Kikusui Seisakusho KK
A tableting machine modified from No. 1 was used to perform compression tableting with a filling amount of 3.1 g per tablet, and 360 stable replenishing tablets for color paper were prepared.

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

The solid processing agent of the present invention is added according to the processing amount of color paper per unit area, and is also replenished with water. The amount of replenishing water is 62.5 ml for the color developing replenisher, and 21.2 ml and 169.9 ml per 1 m ^{2 of} color paper for the bleach-fixing agent and the stabilizer.

The processing amount was 5 m ^{2 of} color paper per day, and the overflow amount was about 3 times that of the tank liquid, and the state of the color development processing tank was observed.

The results are shown in Table 9.

[0175]

[Table 9]

From the results shown in Table 9 above, when the unit supply amount of the solid processing agent was 60 g, a large amount of insoluble matter was present in the color developing tank, and tar was partially generated. Further, when the unit supply amount of the solid processing agent was 0.1 g, the number of times the solid processing agent was charged was abnormally high, the replacement frequency was high, and the workability was significantly lowered.

Also, with respect to the sample No. 107 of Example-2, there were many phenomena in which the sample was not adhered due to a slight adhesion to the packaging material, especially when the unit supply amount was 0.1 g.

[0178]

The weight ratio of the alkali metal hydroxide compound to the carbonate in the solid processing agent is 0.005 to 0.5, and 0.5 to 50 g.
In the solid processing agent prepackaged in (1), the stability and blocking property of the processing agent was improved and the replenishment accuracy was improved by setting the coefficient of friction in the package between the solid processing agent and the surface of the packaging material to 1.5 or less.

[Brief description of drawings]

FIG. 1 is a plan view showing a specific example of a three-sided and four-sided seal packaging.

FIG. 2 is a plan view showing a specific example of stick packaging.

FIG. 3 is a diagram showing a specific example of PTP packaging.

FIG. 4 is a diagram showing a specific example of collective packaging.

FIG. 5 is a diagram showing a specific example of a cartridge.

FIG. 6 is a perspective view showing another specific example of the cartridge.

FIG. 7 is a plan view of the seal packaging.

FIG. 8 is a schematic configuration diagram of a printer processor in which an automatic developing machine and a photo printing machine are integrally configured.

FIG. 9 is a cross-sectional view of a processing agent input unit and a processing agent supply unit of the automatic processor.

10 is a top view of the automatic processor A of FIG.

FIG. 11 is a device for cutting a package into a U-shape and cutting the package.

FIG. 12 is a perspective view of a device for cutting a package into a U-shape.

FIG. 13 is an apparatus showing a method of cutting off a package.

FIG. 14 is a perspective view of the packaging showing the cutting method of FIG.

FIG. 15 is a perspective view of a replenishing device.

FIG. 16 is a side cross-sectional view of a solid processing agent delivery and charging device.

[Explanation of symbols]

 1 Processing Tank 1A to 1E Processing Tank 1R Rack 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 Walls 13 Tablets (Solid treatment agent) 14 Filtration section (category) 15 Package storage box 16 Solid treatment agent package 17 Treatment agent supply means 17a Cutter 17b Conveying roller 17c Ironing roller 23 Preliminarily programmed evaporation replenishment setting means 33 Solenoid valve 35 Drying section 36 Replenishment pipe 42 Replenishment water supply means 43 Replenishment tank

Claims (3)

[Claims] 1. A solid processing for a silver halide photographic light-sensitive material, wherein a weight ratio of the alkali metal hydroxide compound to a carbonate is 0.005 to 0.5 in a processing agent for a silver halide photographic light-sensitive material containing an alkali metal hydroxide compound. An agent, which is preliminarily divided and weighed in 0.5 to 50 g per unit replenishment supply amount, and is packaged in a packaging material having an internal friction coefficient between the solid treatment agent and the surface of the packaging material of 1.5 or less. A solid processing agent package for a silver halide photographic light-sensitive material, characterized in that 2. The solid processing agent package for a silver halide photographic light-sensitive material according to claim 1, wherein the solid processing agent is a granule or a tablet. 3. The solid processing agent package for a silver halide photographic light-sensitive material according to claim 1, wherein the moisture permeability of the packaging material is 50 g / m ² · 24 hr or less.