JPH0743863A - Kit of solid agents for processing silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To prevent the abrasion and damage of the tablets of the solid processing agent at the time of their transportation and to obtain stable photographic performance by specifying the sum of the total weights of the tablets filled in the kit and the hardness of the tablets. CONSTITUTION:The tablets of the solid agent for processing the silver halide photographic sensitive material are applied to an automatic developing machine for processing it and filled in the kit in the direction perpendicular to the diametrical direction in a laminated state, and the sum of their total weight is regulated to 50-500g, and the hardness of the tablets is controlled to 0.6-5.0, and this solid processing agent 1 is filled in a regular row. If the sum of the total weight is <50g, the tablets become easy to flow, and the frequency of exchange of the kit is enhanced and increases the load of users.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a solid processing agent for a silver halide photographic light-sensitive material, and more specifically, it is free from problems such as abrasion and disintegration of a tablet-type photographic processing agent, has improved replenishment accuracy, and has stable photographic properties. The present invention relates to a solid processing agent kit for silver halide photographic light-sensitive materials that provides performance.

[0002]

2. Description of the Related Art A silver halide photographic light-sensitive material (hereinafter referred to as a light-sensitive material) is processed by exposure, exposure, desilvering, washing, stabilization and other steps. Processing is usually carried out by an automatic processor (hereinafter referred to as an automatic processor), in which case the replenisher replenishment method is generally widely used, and the activity of the processing solution in the processing tank is controlled to be constant. There is. In the case of the replenisher replenishing method, the purpose is to dilute the eluate from the photosensitive material, correct the evaporation amount, and replenish the consumption component, and a large amount of overflow liquid is usually discharged due to the supply of the liquid.

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 on the disposal of plastic materials. The development of a new system that eliminates photographic waste liquids and does not use plastic bottles for liquid agents It has been demanded. 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 minilab stores, which have been increasing rapidly in recent years, due to cost reduction and labor shortage, part-timers and feminization are progressing, making it difficult to dissolve or dilute the replenisher.
Accidents due to mis-melting occurred one after another, and many complaints about the replenishment system came to be made.

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

As a method for responding to this demand, Japanese Patent Laid-Open No. 5-11
Japanese Patent Publication No. 9454 discloses a method in which almost all processing components are made into a solid processing agent and directly charged into a processing tank.

Further, Japanese Patent Laid-Open No. 4-213454 discloses a method in which powdery treatment agents are set in an automatic developing machine for each part, and the required amount of each is put into a treatment tank and the powdery treatment agent is automatically prepared. A moisture-proof method with an existing machine is disclosed. However, in this method, after the powdery processing agent is set in the developing machine, the density changes due to its own weight, the predesigned amount cannot be collected, the supply of the replenisher becomes unstable, and the photographic performance changes. I knew that I would do it. 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 charging port 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 greatest drawback of the above method is that the amount taken out changes with the passage of time. See WO91-7332
No. Gazette discloses pressure through package (PT
P) A method is disclosed in which a powdery, granular or liquid treating agent is put into a packaging material and directly put into an automatic developing machine. However, these methods are merely technical disclosures, and do not mention at all the problems of abrasion and disintegration during transportation in actual tablets.

The present inventors have investigated solid treatment agents for these problems, but have not found a true solution.

[0008] In a tablet type solid processing agent kit used in a system for directly replenishing and replenishing in a processing tank dissolving section in an automatic developing machine, injecting failure due to abrasion and disintegration during transportation, resulting decrease in replenishment accuracy and photograph It was necessary to prevent performance fluctuations.

[0009]

SUMMARY OF THE INVENTION The first object of the present invention is to:
It is to supply a solid processing agent kit for silver halide photographic light-sensitive materials, which 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 kit for silver halide photographic light-sensitive materials that significantly reduces the use of plastic packaging materials and enables an environment-friendly low-pollution system.

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

Fourth, there is a supply of a solid processing agent kit for a silver halide photographic light-sensitive material which enables a great reduction of a photographic processing waste liquid by dry replenishment with a solid processing agent.

Fifthly, by supplying a replenishing system of the solid processing agent for silver halide photographic light-sensitive materials, which has a markedly improved replenishing accuracy without the problems of abrasion and disintegration of the tablet-type solid processing agent for photographic light-sensitive materials. is there.

[0014]

The above object of the present invention is a solid processing agent kit applied to an automatic processor for processing a silver halide photographic light-sensitive material. The total weight of the tablet type solid processing agents packed in the kit is 50 g to 500 g, and the hardness of the tablet type solid processing agents is 0.6 to It has been achieved by a solid processing agent kit for silver halide photographic light-sensitive material, which is characterized by being 5.0 (kg / mm).

The present invention will be described in detail below.

The present inventors have carried out enormous experiments on a solid processing agent kit for silver halide photographic light-sensitive materials, and have no problems such as abrasion or disintegration of the tablet type solid processing agent inside the solid processing agent kit during transportation, and the kit. The present invention has led to the invention of a solid processing agent kit which is capable of reliably supplying a tablet-type solid processing agent at the time of use and has excellent compactness.

In the present invention, the solid processing agent kit is filled with a tablet type solid processing agent in the kit, and the tablet type processing agent itself is divided and weighed, and dissolved according to the capacity of the replenishment tank. It was found that the number of tablets to be used can be selected arbitrarily and that it has excellent properties for the working environment because it does not generate dust.

In particular, it has been found that the method of directly charging the solid processing agent into the tank of the processing tank for the automatic developing machine is effective in that the weighing means is not required in the automatic developing machine and the apparatus can be made compact.

However, in the case of the tablet type solid treatment agent kit of the present invention, there is a problem that the tablet inside is worn or disintegrated due to the impact during the transportation of the kit, and as a result, a tablet abrasion product or It was found that disintegrants accumulated and the active ingredient as a treating agent was not sufficiently supplied, which had an effect on the treating performance.

In order to solve this problem, the present inventors have
As a method of increasing the hardness of the tablet itself, a method of adding a known binder to the tablet or a method of increasing the tableting pressure during the tableting process was examined, but in the former, the binder itself affects the photographic performance. The amount of the active ingredient per tablet is low because it is applied or a large amount is required, which causes a problem of inefficiency.The latter causes deterioration of tablet solubility when the tableting pressure is excessively increased, and affects the tableting machine. It was found that there was a problem that the load increased and manufacturing problems occurred, and none of these could solve the problem.

Here, the present inventors have noticed that abrasion of tablets occurs due to repeated contact between tablets and tablets or tablets and packaging materials during transportation by vibration during transportation, and the tablets are aligned. It has been found that the packaging of the tablet in such a state can suppress the degree of freedom of the tablet in the kit and greatly reduce the abrasion of the tablet.

Further, the inventors of the present invention have conducted further studies and found that even in the packaging form in which the tablets are stored in an aligned state, there is an important relationship between the total weight of the tablets filled in the kit and the tablet hardness. It was

That is, at least the tablet-type solid processing agent is stored in the kit in an aligned state, and the total weight of the tablet-type solid processing agent filled in the kit is 50 to 500 g.
Furthermore, the hardness of the tablet-type solid processing agent in the kit is 0.6 to 5.0.
It has been found that the effects of the present invention can be achieved in a solid processing agent kit for a silver halide photographic light-sensitive material, which is characterized by being (kg / mm). The total weight of the tablets in the kit is
If the amount is less than 50 g, the tablets may easily flow inside the kit, and the vibration of the tablets may cause abrasion to cause extremely large problems. Furthermore, considering the replacement frequency of the kit, the tablets in the kit may be damaged. If the total weight of is less than 50 g, it requires 200 to 300 g per 1 m ² processing of silver halide photographic light-sensitive material like tablets for fixing solution, so that the kit replacement frequency becomes very high and the user's load becomes large. It turns out that another problem arises.

The total weight of tablets in the kit is 500 g.
In the above case, it was found that the tablets at both ends aligned by the impact such as a drop are unnecessarily loaded and the tablets are broken. In addition, the compactness of the kit is lost, which causes a problem as a commercial value.

Furthermore, the total weight of the tablets in the kit is 50
The present inventors have found that even in the range of g to 500 g, a serious problem occurs depending on the filling number of tablets stored in an aligned state.

In the tablet kit stored in an aligned state, the sum of the total weight of the filled tablets applies a load to the tablets at both ends of the kit, and as a result, the tablets at both ends are vibrated due to vibration during transportation. It was found that the wear was severe and a problem occurred.

The inventors of the present invention have made extensive studies and found that when the total weight of the tablets in the kit is in the range of 50 to 500 g and the hardness of the tablets is 0.6 to 5.0 (kg / mm), It has been found that the wear on the tablets at both ends can be minimized.

When the tablet hardness is 0.6 (kg / mm) or less,
As described above, the load of the filled tablets not only causes wear on the tablets at the end of the kit but also causes a problem that the tablets are broken due to an impact such as dropping. Tablet hardness
If it is 5.0 (kg / mm) or more, there is no problem with the impact due to dropping, but the hardness becomes excessively strong, and the impact absorption capacity of the tablet itself decreases when the tablets contact each other due to the impact. It was found that the edge part of the was damaged, resulting in severe abrasion.

The present invention will be further described in detail.

The tablet referred to in the present invention can have any shape, and examples thereof include a cylindrical shape, a disk shape, a square plate shape, and a triangular plate shape. From the viewpoint of productivity and handleability, cylindrical and disk-shaped tablets are preferable.

In the case of the disk-shaped or cylindrical tablet, the length in the longitudinal direction of the tablet refers to the diameter of the tablet, but the diameter at this time can be any value depending on the purpose of use. From the viewpoint of productivity, it is preferably 5 to 60 mm, more preferably
It is 10-40 mm. On the other hand, the ratio (x / h) of the length (x) to the thickness (h) in the elongate direction of the tablet is preferably in the range of 1.0 to 6.0, more preferably 2.5 to 5.0. When the above ratio is less than 1.0, the thickness of the obtained tablet increases, the solubility deteriorates and the productivity also deteriorates. If it exceeds 6.0, the desired strength cannot be obtained.

The hardness of the tablet in the present invention is defined by the following formula.

Tablet hardness = tablet crush strength (kg) /
The length of the tablet in the major axis direction (mm) The compressive breaking strength of the tablet is the breaking strength when pressure is applied to the major axis of the tablet. Monsanto hardness meter, Stokes hardness meter, speed checker (Okada Seiko Co., Ltd.) ) Etc. can be measured using a commercially available device or the like.

The solid processing agent according to the present invention may be used in any method according to the purpose, but from the viewpoint of downsizing of the automatic developing machine, reduction of processing waste liquid, etc., the processing tank of the automatic developing machine. It is preferable to directly add to the above as a replenisher.

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

To solidify the photographic processing agent, a concentrated liquid or fine powder or granular photographic processing agent and a water-soluble binder are kneaded and molded, or the water-soluble binding agent is formed on the surface of the temporarily molded 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 Publication No. 09). A preferable method for producing a tablet is to form a powdery solid processing agent by granulating and then performing a tableting step. There is an advantage that the solubility and the storability are improved and the photographic performance becomes stable as compared with the solid processing agent formed by the tableting step by simply mixing the solid processing agent components.

As the granulation means for tablet formation, known means 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, the components become nonuniform, so-called segregation does not easily occur. It is preferable to use one, more preferably 200 to 750 μm
Is. Furthermore, the particle size distribution is ± 10 for 60% or more of the granulated particles.
Those within a deviation of 0 to 150 μm are preferred. 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, during granulation, the above-mentioned effect becomes more remarkable by separately granulating each component, for example, an alkali agent, a reducing agent, a bleaching agent, a preservative and the like. Alternatively, by using a multilayer tablet, the above effect becomes more remarkable.

The means for producing the tablet-type treatment agent is generally described in the specifications such as JP-A-51-61837, JP-A-54-155038, JP-A-52-88025, and British Patent 1213808. It can be produced by any means, and the granule treating agent can be produced by, for example, JP-A-2-090.
It can be produced by a general method described in the specifications of Nos. 42, 2-109043, 3-39735 and 3-39739. Further, the powder processing agent can be produced by a general method as described in the specifications of JP-A-54-133332, British Patent Nos. 725892 and 729862, and German Patent No. 3733861. The means for producing a multilayer tablet can be produced, for example, in the case of a three-layer tablet, by referring to the means described in "Development of Pharmaceuticals Volume 11 P78-79".

The solid processing agent kit of the present invention is preferably further moisture-proof packed. 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 (20 ° C. 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.

The solid processing composition of the present invention is arranged and stored in a columnar container. The shape of the columnar container is a cylindrical shape, and the solid processing agent is stored inside the cylinder, for example, one end is completely closed and the other can be released when using the kit, or when set in an automatic processor. It is designed to be an opening. The bottom surface of the columnar container has a circular shape, a triangular shape, a quadrangular shape, or the like, but has a shape close to the shape of a tablet. The material of the columnar container may be any of paper, polyvinyl chloride, polyethylene, polypropylene, polyester and composite materials.
Further, for example, aluminum vapor deposition of the above materials may be used.

The solid processing agent kit of the present invention is the effect of the present invention, and from the viewpoint of preventing breakage of tablets during transportation, the inside of the container having a surface cut perpendicular to the alignment direction of the solid processing agent in the columnar container. Of the circumscribed circle of the solid treatment agent and the diameter of the circumscribed circle of the solid processing agent
Is preferably R / γ ≦ 1.20, and more preferably R / γ ≦ 1.10.

[0048]

【Example】

Example 1 A solid processing agent for a color negative film was prepared as shown below.

Color development replenishing tablet for color negative film Operation (1) 70 g of a developing agent CD-4 (4-amino-3-methyl-N-ethyl-N-β-hydroxyethylaniline sulfate) in a commercial Van Dam mill Grind until the average particle size reaches 10 μm. This fine powder was granulated in a commercially available 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. The water content of the granulated product was almost completely removed to prepare granules (A) for color development replenishment for color negative.

Operation (2) 69.4 g of hydroxylamine sulfate and 4 g of pine flow (manufactured by Matsutani Chemical Co., Ltd.) were pulverized in the same manner as in operation (1), and then mixed and granulated. The amount of water added 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 (B) for color development replenishment for color negative.

Operation (3) 1-hydroxyethane-1,1-diphosphonate disodium 15
g, potassium sulphite 72.8g, potassium carbonate 350g, sodium hydrogen carbonate 3g, sodium bromide 3.7g and mannite 22g, polyethylene glycol 6000 5.0g are crushed and mixed in the same manner as in the operation (1), and the amount of water added is 40 ml. And granulate. 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 developing replenishing granules (C) for color negative.

Color development replenishing granules (A) to (C) for color negative described above are mixed, and 2 g of sodium N-lauroylalanine is added to the granulated product thus prepared.
Mix evenly for 10 minutes using a mixer in a room where the temperature is controlled to ℃ and 40% RH or less. Next, the mixture was compressed into tablets using a tableting machine modified from Tough Pressed Collect 1527HU manufactured by Kikusui Seisakusho Ltd., changing the diameter and filling amount of each tablet as shown in Table 1. A development replenishment tablet D was prepared.

The tablets D were arranged and stored in a polyethylene cylindrical container having an inner diameter of 32 mm as shown in FIG. The container was filled with tablets D in the numbers shown in Table 1, and shaken at a stroke width of 60 mm using a shaker at 200 times per minute to observe the tablet state after 24 hours and before and after the shaker test. The change in tablet weight in the container was measured.

The filling rate of the container was adjusted to 70% by changing the height.

The evaluation of the appearance change of the tablets is as follows.

Evaluation of Change in Appearance of Tablets XX: Wear of tablets in the kit is severe and the original shape is not maintained. X: Dust is generated at opening due to wear of tablets in the kit. ◯: Dust at opening without any problem in appearance. There is no problem. Tables 1 and 2 show the results.

[0057]

[Table 1]

[0058]

[Table 2]

As is clear from Tables 1 and 2, the anti-friction effect of the tablet, which is the effect of the present invention, is such that the total weight sum of the tablets packed in the kit is in the range of 50 g to 500 g and the tablet hardness. Is 0.6 to 5.0 kg / mm, preferably 1.0 to 3.0 kg / mm
It is understood that it is played in the case of.

Example 2 FIGS. 2 (a) and 2 (b) show an example of the tablet type solid processing agent storage container of the present invention. FIG. 2A shows a perspective view of the storage container. The storage container 3 is made of a resin molded product, and the heat-sealing member 4 shields the tablet-shaped solid processing agent outlet 5 on the bottom surface having the opening shape to provide a moisture-proof seal.

FIG. 2 (b) is a sectional view of FIG. 2 (a), and the tablet type solid processing agent 1 is stored in a plurality of rows. By peeling the heat-sealed heat-sealing member 4 from the storage container 3, the tablet-type solid processing agent 1 moves from the take-out port 5 to the supply port 7 of the supply-moving plate 6, and further the supply-moving plate 6 Moves and is dropped by its own weight into the supply port of the supply device 8.

The same experiment as in Example 1 was carried out by replacing the polyethylene plastic columnar container of Example 1 with an integrally shaped polyethylene plastic container 3 in which the columnar containers shown in FIG. It has been found that even when the columnar containers are arranged in parallel, the effect of the present invention can be obtained even when the columnar containers are arranged in parallel by applying the configuration of the present invention to one columnar container.

[0063]

The solid processing agent kit for silver halide photographic light-sensitive material of the present invention has an effect of preventing abrasion and damage of tablets due to vibration during transportation of the kit, and the generation of dust during use of the kit and necessary components It is possible to prevent troubles such as not being charged in a predetermined amount and obtain stable photographic performance.

[Brief description of drawings]

FIG. 1 is a perspective view of a columnar container of a solid processing agent kit.

FIG. 2 is a perspective view and a sectional view of a triple-type solid processing agent kit.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Solid processing agent 2 Columnar container 3 Triple storage container 4 Heat seal member 5 Outlet 6 Supply moving plate 8 Supply device

Claims (1)

[Claims] 1. A solid processing agent kit applied to an automatic processor for processing a silver halide photographic light-sensitive material, in which at least a tablet type solid processing agent is laminated in a direction perpendicular to a diameter direction. The total weight of the tablet-type solid processing agent stored in the kit is 50 g to 500 g, and the hardness of the tablet-type solid processing agent is 0.6 to 5.0 (kg /
mm) is a solid processing agent kit for silver halide photographic light-sensitive materials.