JPH06295029A - Solid processing agent package for silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To replenish a processing agent with high precision by specifying the friction coefficient between a specified weight of the agent contg. p- phenylenediamine derivative and enclosed in a package and the packaging material. CONSTITUTION:A solid processing agent contg. a p-phenylenediamine derivative is weighed into a unit supply of 0.5-50g and packaged with a packaging material with the friction coefficient between the agent surface and the packaging material surface controlled to <=1.5. A compd. (D-1) given in the Patent application No. 4-209834, etc., are used as the derivative, the processing agent is tableted, granulated or powdered, and the tablet and granule are preferably used from the viewpoint of preservability and the amt. remaining in the packaging material. A synthetic resin such as PE and PP having a moisture permeability of 50g/m.24hr (40 deg.C.90% RH) is preferably used for the packaging material.

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 package for a silver halide photographic light-sensitive material, and more particularly to a solid processing agent for a silver halide photographic light-sensitive material which provides stable photographic performance with improved replenishment accuracy. Regarding packaging.

[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. In addition, the development of exposure control technology for printing has progressed in the minilab store, which has been increasing rapidly in recent years, and a system that allows anyone to print has been introduced. However, the work of dissolving the replenisher and the management of the treatment liquid are still difficult, and very serious mistakes such as mistakenly dissolving and replenishing the treatment agent are likely to occur. There have been many complaints about this conventional replenishment system.

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 to meet this demand, WO92 / 2001
Japanese Patent Publication No. 3 discloses a method in which almost all processing components are made into a solid processing agent and directly charged into a processing tank. However, in this method, since the solid processing agent is directly charged into the processing tank, the processing agent adheres to the photosensitive material to be processed, causing an accident, or absorbing the evaporated water from the processing tank or the water in the atmosphere,
The solid processing agents stick to each other and the solid processing agents are not reliably added to the processing tank, or they adhere to the packaging material and the loading accuracy and weighing accuracy are significantly reduced. For example, inaccurate replenishment is possible, and when a para-phenylenediamine derivative is present in the solid processing agent, it partially oxidizes due to air oxidation over time regardless of the packaging condition, and in addition tar generation occurs. It was also found that there are problems related to storage, such as blocking of the solid processing agent, which is presumed to be the main cause, and inaccuracy of the charging accuracy at the time of replenishment due to tar, etc., which seriously affect photographic performance.

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 powdery chemical is set in the hopper of the charging device, the density changes due to its own weight and each part is not designed in a predesigned amount and the replenishment of the replenisher is not constant. It turned out that performance changed. Even if the evaporation water from the upper part of the processing tank is prevented to some extent, the problem of sticking of the powdery processing agent at the inlet due to moisture absorption is inevitable, and the set powdery processing agent is left in the atmosphere. Therefore, the powdery treatment agent is blocked and adhered to the packaging material, so that it cannot be accurately weighed.

As described above, the biggest drawback is that the amount of preparative change changes with the passage of time.

Further, WO91 / 7332 discloses a method in which a powder, granule or liquid processing agent is put in a pressure through package (PTP) packaging material and directly put into an automatic developing machine. However, this method merely discloses a replenishment method in which a solid processing agent and a chemical which cannot be solidified are directly charged into a processing tank in order to promote low-concentration replenishment. Or moisture absorption over time when packaged separately, especially solid treatment agents containing para-phenylenediamine derivative are easy to adhere to the packaging material and remain in the packaging material. There is no suggestion of solving the problem.

Further, since PTP itself opens the packaging material by pressure, powder is likely to scatter and adheres to the wall of the processing tank to cause tar and the like, and the scattered powder jumps into other processing tanks. It was also found that it could cause contamination. It was also found that when opened by pressure, a piece of packaging material was introduced together with the solid processing agent to induce clogging of the filter.

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.

[0012] However, as a result of diligent studies, it was found that the solid processing agent of one replenishing unit was prepackaged in a replenishing unit of 0.5 to 50 g, and the packaging contained the paraphenylenediamine derivative. As long as it is packaged with a packaging material that maintains the internal friction coefficient between the surface of the contained solid treatment agent and the surface of the packaging material to be 1.5 or less, even if the solid treatment agents are stored at a humidity of 80% for about 2 years, No blocking, no adhesion of the solid processing agent to the packaging material, and no generation of tar.

It has also been found that when the container is opened and dropped by gravity, it is surely replenished without any residue so that stable photographic performance can be obtained with minimum fluctuation in the concentration of the working solution.
In addition, they have found that melting work is free, ease of setting in an automatic developing machine, no erroneous melting, contamination is prevented, and various problems related to replenishment are solved.

[0014]

SUMMARY OF THE INVENTION An object of the present invention is, firstly, to provide a solid processing agent package for a silver halide photographic light-sensitive material, which has an accurate replenishment amount.

Secondly, solid processing for silver halide photographic light-sensitive materials is made possible by eliminating liquid chemicals that pose dangers in transportation and handling, and by making it possible to use solid chemicals without complicated operations for users. To provide an agent package.

Thirdly, a solid processing agent package for a silver halide photographic light-sensitive material is provided which eliminates the mixing and dissolving work of the concentration kit with water by the user himself and completes the replenishing system of the fully automatic solid processing agent. To do.

Fourth, eliminating many built-in refill tanks,
An object of the present invention is to provide a solid processing agent package for a silver halide photographic light-sensitive material to be used in a compact automatic processor.

Fifth, to provide a solid processing agent package for a silver halide photographic light-sensitive material, which eliminates the need for storing a liquid replenisher, improves processing stability and reduces the amount of chemical waste solution.

A sixth object of the present invention is to provide a solid processing agent package for a silver halide photographic light-sensitive material, which achieves a low-pollution system by reducing the plastic packaging material without using a plastic bottle for liquids.

[0020]

In order to solve the above problems, the inventors of the present invention have found that the following constitution can be achieved.

In a package of a solid processing agent for silver halide photographic light-sensitive material, the solid processing agent is 0.5 per unit replenishment supply amount.
Pre-divided and weighed in the range of ~ 50g, containing at least para-phenylenediamine derivative, and the outside of the solid processing agent is packaged with a packaging material having a friction coefficient of 1.5 or less in the packaging between the surface of the solid processing agent and the surface of the packaging material. This is achieved for the first time by a solid processing agent for silver halide photographic light-sensitive materials.

Granules and tablets are preferred embodiments of the package in view of the effect of the present invention.

[0023]

The present inventors have found an optimum solid processing agent replenishment amount to be added at one time in order to prevent the photographic performance of each processing solution from changing with regard to directly adding the solid processing agent to the processing tank. It was thought that this optimum replenishment amount depended on the size of the processing tank of the automatic processor, that is, the capacity of the processing solution, but by making good use of the characteristic that the solid chemical is difficult to dissolve,
It has been found that the concentration does not rise sharply even if added all at once, and that replenishing water can be injected in tandem with dissolution, which has the advantage of creating extremely stable photographic performance.

The packaging material is affected by temperature and humidity with the passage of time, and not only the coefficient of friction in the package with the surface of the solid processing agent changes, but also wrinkles occur in the packaging material, and powders, granules and tablets which are solid processing agents are wrinkled. It was found that it became difficult to fall into the treatment tank by itself.

The amount of the processing agent added at one time is preferably 0.5 to 50 g, and particularly preferably 1 to 20 g in the color developer. The friction coefficient in the packaging is 1. so that the solid treatment agent containing para-phenylenediamine in this range becomes one replenishment unit.
For the first time, it was found that stable photographic performance can always be maintained when the product is directly packaged in a part of the processing tank of a general small-sized developing machine by processing with a packaging material that maintains 5 or less and is processed while slowly dissolving. .

It was found that the solid treating agent was always added in a predesigned amount without being affected by the storage of the solid treating agent with time.

The present invention will be specifically described below.

In the present invention, the term "per unit replenishing and supplying amount of the solid processing agent" refers to the total weight of the solid processing agent added at one time when a certain amount of the silver halide photographic light-sensitive material is processed. That is, if too much unit replenishment and supply is added to the processing tank of the solid treatment agent, dissolution failure of the solid treatment agent tends to occur, and if the unit replenishment and supply amount is small, a certain amount of solid treatment agent is supplied. Since the number of times of charging of the container increases, the accuracy of charging and the durability of the supply means also 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 1.0.
It is the following. 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 sealed. At a temperature of 25 ° C and a relative humidity of 40%, the packaging materials a and b shown in Fig. 8 were cut to obtain "Static Frict" manufactured by HEIDON.
Using ionTester HEIDON-10, fix the packaging material together and measure tan θ at which 80% or more of the solid processing agent slips off the packaging material. This tan θ is called the in-packaging friction coefficient between the surface of the solid processing agent and the surface of the packaging material.

The friction coefficient in the package varies depending on the surface property, components, size and shape of the solid processing agent, the material of the packaging material, the surface roughness, and the storage condition. The object of the present invention is achieved for the first time by the packaging material in which the coefficient of friction in the packaging between the materials achieves 1.5 or less at the time of packaging and the solid processing agent which is pre-divided and weighed in the range of 0.5 to 50 g per unit replenishment supply amount is packaged. can do.

Accordingly, any packaging material may be used as long as the combination of the surface of the solid processing agent and the surface of the packaging material achieves a coefficient of friction in the package of 1.5 or less. Materials are preferably used, specifically, polyethylene, polypropylene, polyvinyl chloride,
Examples thereof include polyvinyl acetate, nylon, polyvinylidene chloride, polystyrene, polycarbonate, vinylon, and polyethylene terephthalate. They may be a single film or laminated with two or more kinds of films, or aluminum foil between the films. May be used.

The packaging material of the present invention has an internal friction coefficient of 1.5 or less with the surface of the solid processing agent. Furthermore, the moisture vapor transmission rate is 50g /
The effect of the present invention becomes more remarkable when the temperature is m ² · 24hr (40 ° C · 90% RH) or less. In other words, when the moisture 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, and the coefficient of friction within the package. It is because it also affects. A packaging material having a moisture permeability of preferably 20 g / m ² · 24 hr (40 ° C. 90% RH) or less is preferably used in the embodiment of the present invention.

The thickness of the packaging material is 1 to 500 μm in terms of usability, disposal of the packaging material, friction, and moisture permeability.
It is more preferably 10 to 150 μm.

As a method for packaging the solid processing agent, there are four-sided seal, three-sided seal, stick (pillow package, gusset package), PTP (blister package), cartridge, and the like.

When the peel-open method is used as the unsealing and charging means, a sealant agent can be laminated to provide the peel-open suitability.

As a method of supplying the solid processing agent to the processing tank, there is a method of opening and taking out the package, but a method of separating the adhesive surface (peel open) at the time of opening, and making a cut in a part of the seal package and pulling Therefore, a method of opening the package, a method of cutting by an external force of a cutter, a method of forcibly pushing out the solid processing agent, and the like are preferably used. When the solid processing agent is a tablet, the dulma removing method is also preferably used.

The solid processing agent in the present invention means tablets, granules and powders. Tablets and granules are preferred for the storage stability of the solid processing agent and the accuracy of one-time loading, in view of the residual rate in the packaging material.

The powder in the present invention refers to an aggregate of fine crystal grains.

The granules referred to in the present invention are obtained by adding a granulation step to powders, and are particles having a particle size of 50 to 5000 μm.
It is preferably 500 to 1500 μm. If it is small, it tends to remain in the packaging material at the time of loading and is easily scattered, and if it is large, fine powder particles are likely to be formed during transportation.

The tablet referred to in the present invention refers to a powder or granule obtained by compression-molding a certain shape.

The para-phenylenediamine derivative used in the present invention is described in Japanese Patent Application No. 4-209834, paragraph [0023],
[0026], [0027], [0036] [003
7] [0038] [0039] [0040] [004
1] The compound described in [0042] is used, preferably [D-1], [D-2] [E-2], and most preferably [D-1] [D-2].

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 tablet formation, known methods such as rolling granulation, extrusion granulation, compression granulation and fluidized bed granulation can be used. % Is ± 100
It is preferable that the deviation falls within a range of up to 150 μm from the viewpoint of input accuracy.

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
Can be produced by a known method or the like, and granule treating agents are disclosed in JP-A Nos. 2-109042, 2-109043, 3-39735 and 3-397.
No. 39, etc.
54-133332, British Patents 725,892 and 729,862, and German Patent 3,733,861 can be manufactured by known methods.

Next, an automatic developing machine equipped with a feeding device for using the solid processing agent of the present invention will be described.

FIG. 1 shows a cross section of an automatic processor equipped with a charging device. 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. In addition, in this example, a case where a tablet is used as a solid processing agent will be described.

The processing bath 1 for processing the photosensitive material is a solid processing agent feeding section 4 for supplying a solid processing agent (tablet) integrally provided outside the partition wall forming the processing tank 1 and a constant temperature bath 2.
Have. The processing bath 1 and the constant temperature bath 2 are partitioned by a partition wall 21 having a communication window formed therein, so that the processing liquid can flow. Since the enclosure 5 for receiving the solid processing agent is provided in the charging section 4 provided above the constant temperature tank 2, the solid processing agent does not move to the processing tank 1 in a solid state. It should be noted that the enclosure 5 has a mesh-like or filter-like shape that allows the treatment liquid to pass therethrough, but does not allow the solid treatment agent to pass until it is dissolved.

The cylindrical filter 22 is provided below the constant temperature bath 2 so as to be replaceable, and has a function of removing insoluble matter such as paper waste in the treatment liquid. Inside this filter 22,
It is connected to the suction side of the circulation pump 24 (circulation means) via a circulation pipe 23 provided through the lower wall of the constant temperature bath 2.

The circulation system is composed of the circulation pipe 23 forming the liquid circulation passage, the circulation pump 24, the processing tank 1 and the like. The other end of the circulation pipe 23, which communicates with the discharge side of the circulation pump 24, penetrates the lower wall of the processing tank 1 and communicates with the processing tank 1. With such a configuration, when the circulation pump 24 is operated, the processing liquid is sucked from the constant temperature tank 2 and discharged to the processing tank 1, and the processing liquid mixes with the processing liquid in the processing tank 1 and returns to the constant temperature tank 2 again. The cycle of entering will be repeated. The flow rate of the circulation flow 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.
It is rotation. Further, the circulation direction of the processing liquid is not limited to the direction shown in FIG. 1 and may be the opposite direction.

The waste liquid pipe 31 is used for overflowing the processing liquid in the processing tank 1. The waste liquid pipe 31 keeps the liquid surface level constant, and the 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 25 is arranged so as to penetrate the upper wall of the constant temperature bath 2 and be immersed in the treatment liquid in the constant temperature bath 2. The heater 25 heats the treatment liquid in the constant temperature bath 2 and the treatment bath 1, in other words, keeps the treatment liquid in the treatment bath 1 within a temperature range suitable for the treatment (for example, 20 to 55 ° C.). It is a temperature adjusting means.

The processing amount information detecting means 32 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 32 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 32 may be any one capable of detecting the width and the conveying time of the photosensitive material such as an infrared sensor, a micro switch, an ultrasonic sensor. Further, the detected information may be a value that is proportional to the processing amount of the processed, processed, or being processed photosensitive material, such as the concentration of the processing liquid stored in the processing tank or the change in the concentration. It may be.

In FIG. 1, 6 is a container for accommodating a solid processing agent package, 9 is a second conveying means for conveying the package, and 16 is a processing agent in response to a signal from the processing amount information detecting means 32. It is a control means for controlling the supply of the throughput.

FIG. 2 is a perspective view for explaining in detail the concrete structure of the seal packaging material opening / closing device 3, and FIG. 3 is a perspective view in which the viewing angle is further changed, and is also a block diagram showing the configuration.

In FIG. 2, the container 6 for accommodating the solid processing agent package accommodates the solid processing agent package H with its belt portion meandering. , The roller 8-a, the roller 8-b and the first conveying means 8 including the driving means, or the lid 7 is opened to guide the roller 9-a, the roller 9-b and the driving means. The second transfer means 9 is provided, and the lid 7 is closed.
The second transporting means 8 and the second transporting means 9 are engaged with each other. The second
Cutting means (cutter) 10 before engaging with the conveying means 9 of
By this, the upper and lower seal parts are separated and guided in the direction of arrow A to be removed.

Next, as shown in FIG. 3, the packaging portion H-b, in which the seal portions on both the upper and lower sides are separated and the upper and lower sides are opened,
Since the mutual relationship between the first transporting means 8 and the second transporting means 9 is controlled so that the remaining girder-shaped seal portions are brought close to each other, the bulge of the packaging portion H-b is emphasized as shown in the figure,
Since the sandwiching of the solid processing agent T is released, the solid processing agent T
Falls. In FIG. 2, the guide 12 guides the progress of the band-shaped solid processing agent package H and regulates the position where the processing agent falls due to the bulge, whereby the inlet 13 does not have to be huge.

In this embodiment, the cutting means (cutter) 10 is a disk-shaped rotary cutter, but it is not limited to this. For safety, the cutter blade is preferably configured to be replaced as a set as the cutter tip 11.

As shown in FIGS. 2 and 3, the rollers 8-b,
The roller 9-b is a notched roller by removing a part of each cylinder, and since the axial distance of each roller pair is fixed, rotation of the roller pair causes the notched portion to be the roller 8-. When facing a or the roller 9-a, the nip pressure between both rollers is lost and the nip pressure is reduced.
The sandwiched strip-shaped solid treatment agent package H can freely move in the plane direction, and can return to the center, for example, when it starts to meander.

The detection means 14 in FIG. 3 detects the detected portion 15 for each package recorded on the side end of the solid processing agent package H, sends a signal to the processing amount supply control means 16, and drives the motor. It controls and drives the 1st conveyance means 8 and the 2nd conveyance means 9.
It also indicates that it is also used to display the remaining amount.

Next, referring to FIG.
A situation in which the feeding speed of the conveying means 9 is low and the belt-shaped solid processing agent package H is bulged due to the difference in the feeding speed will be described. In FIG. 5, the same gears are fixed to the roller shafts of the first conveying means 8 and the second conveying means 9, and common gears are used.
Since the shafts are driven at the same time by 18, the number of rotations of the shaft is the same, but the rollers 9-a and 9-b of the second conveying means 9 have a smaller diameter than the rollers of the first conveying means 8 and therefore have a peripheral speed. Becomes smaller and the feed rate is slow.

The timing chart shows that the first and second conveying means are simultaneously driven.

Next, in FIG. 5, the second conveying means 9 is
An embodiment in which the transport means 8 is driven simultaneously with the transport means 8 and is then temporarily reversed. In this embodiment, the feeding speeds of the first conveying means 8 and the second conveying means 9 are the same, but the rotation of the second conveying means 9 which is reversed after the stop causes the belt-shaped solid treatment agent package H to be removed. The slack that is returned and the portion that sandwiched the solid processing agent T swells, and the solid processing agent T is released.

Next, FIG. 6 shows an embodiment in which the phases of action of the first conveying means 8 and the second conveying means 9 are different. Since the first transfer means 8 is first driven by the movable drive source 19 and then the second transfer means 9 is driven, the strip-shaped solid processing in which the seal parts on both sides are separated by the first transfer means. The girder-shaped seal portion preceding the packaging portion of the agent package H is
The second transport means 9 is reached, but still the second transport means 9
Is stopped because it is not driven, and solid processing agent package H
The sagging occurs in the bag, and the packing portion is inflated to release the solid processing agent T.

FIG. 7 shows a control flow chart of the supply operation regarding the dropping of the solid processing agent. That is, the remaining amount of the processing agent is checked by the processing information signal, and if there is no remaining amount, a signal indicating no remaining amount is output. If there is a remaining amount, the supply operation is started and the motor is driven. Then, the completion of the supply operation for one time is checked, and if the supply operation is completed, the supply operation is stopped, but if not completed, the motor M is driven again and the supply operation is repeated.

[0066]

【Example】

Example 1 A treatment agent for a color negative film shown below was prepared, and the packaging materials shown in Table 1, Table 2 and Table 3 were used to seal on four sides and packaged.

(1) Powder processing agent for color developing replenisher for color negative film Developing agent CD-4 [4-amino-3-methyl-N-ethyl-N-β-
(Hydroxy) ethylaniline sulfate 150 g, potassium hydroxide 31.8 g, sodium sulfite 134.5 g, hydroxylamine sulfate 69.4 g, potassium bromide 9.9 g, diethylenetriaminepentaacetic acid 42.9 g, potassium carbonate 375 g, pine flow
4.6 g and 90 g of mannite were crushed in a commercially available bandam mill to an average particle size of 10 μm, and these materials were uniformly mixed for 10 minutes using a mixer in a room whose humidity was controlled to 40% RH or less, This was divided into 280 equal parts to prepare 280 powder processing agents (I) for color development replenishment for color negative. (Hereinafter referred to as solid processing agent (1)) (2) Granular processing agent for color development replenishment for color negative film Operation (a) Developing agent CD-4 [4-amino-3-methyl-N-ethyl-N-β-
150 g of (hydroxy) ethylaniline sulphate is ground in a commercial bandam mill to an average particle size of 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 a color negative film.

Procedure (b) 69.4 g of hydroxylamine sulfate and 4.6 g of pine flow were pulverized in the same manner as in procedure (a), 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 film.

Operation (c) Potassium hydroxide 31.8 g, sodium sulfite 134.5 g, potassium bromide 9.9 g, diethylenetriaminepentaacetic acid 42.9
g, 375 g of potassium carbonate and 90 g of mannitol are pulverized and mixed in the same manner as in step (a), and the amount of water added is 40 ml, and granulation is performed. 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 (c) for a color negative film.

The above-mentioned color development replenishing granules for color negative film (a), (b) and (c) were mixed and divided into 280 equal parts.
Granules for replenishing color development for 280 color negative films (I
I). (Hereinafter referred to as solid processing agent (2)) (3) Color development replenishing tablet for color negative film Mixed granules (II) made by operations (a), (b) and (c)
Kikusui Seisakusho Co., Ltd.'s Tough Press Collect 1527HU remodeled tableting machine with a filling amount of 5.0 g per tablet and compression tableting for 280 color negative film color development replenishing tablets (III) ( Hereinafter, a solid processing agent (3) was prepared.

After packaging the solid treating agent prepared above with the packaging materials shown in Tables 1, 2 and 3, the temperature was 40 ° C. and the relative humidity was 40 ° C.
60% (condition 1) temperature 5 ° C. Relative temperature 20% (condition 2) were alternately repeated every 6 hours and stored for 15 days.

The friction coefficient in the package was measured by the method described in the present specification. The results are summarized in the table below. Further, the seal packing material unsealing and charging device was charged by using FIG. 3, and the weight (%) of the solid processing agent adhering and remaining in the packaging material to the divided and weighed solid processing agent was determined.

[0073]

[Equation 1]

The results are shown below.

[0075]

[Table 1]

[0076]

[Table 2]

[0077]

[Table 3]

As is clear from the above table, when the friction coefficient in the package is smaller than 1.49, the residual rate of the solid processing agent in the package decreases. Further, it can be seen that the value of 1.00 or less is more preferable. In addition, it can be seen that the tablet, the granule, and the powder are placed in this order in good accuracy.

In the above table, "unmeasurable" means that the coefficient of friction in the package exceeds 1.5. The sealing method is shown in FIG.

Even when changing from (A) to (B), (C) and (D), the residual rate of the solid processing agent was the same. In this seal / packaging material unsealing / charging device, the four-way sealing methods (A), (B), and (C) shown in FIG. 9 are preferable from the viewpoint of unsealing and transportability, and (A) is preferable from the viewpoint of packaging material cost.

Further, as a method for sealing and packing tablets and granules, there is a 4-way seal 3-way seal stick (pillow package, gusset package) PTP cartridge.

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

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

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

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

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

In the peel open method using the film of the present invention, the interlaminar peeling method or the interfacial peeling method is preferable.

FIG. 10 shows an example of a carton for storing a continuous package containing these solid processing agents.

FIG. 11 shows a preferred form of the solid processing composition of the present invention. A, B, C and D are solid processing agents.

(A) shows a form in which the maximum diameter of a tablet having the same composition is different because the solubility is controlled with a tablet solid processing agent. (B) shows a packaging material divided according to the type of drug, and a single injection Sometimes the solid processing agents A, B and C are packed so that they can all be put in once. (C) is a form in which the solid processing agents of powder or granules or a mixture of powder and granules that are thrown in at one time are packed. (D) shows a form in which one tablet treatment agent is added at one time. (E) shows a form in which three tablet treatment agents are added at one time. (F) shows , The solid processing agent of powder or granules or a mixture of powder and granules, which is charged at one time, is separately packaged for each chemical, and is further divided into two because there are many A agents. (G) is charged at one time. (H) shows the form in which the solid processing agent of powder or granules or a mixture of powder and granules is packaged for every four chemicals. The powder or granules to be thrown in once and the solid processing agent of the mixture of flour and granules are made into two parts, each of which is contained in 2 packages. (I) is a tablet to be thrown in once (J) shows the morphology when there are three tablets (J) shows the morphology when there are four tablets to be thrown at once (K) shows the morphology when there are four tablets to be thrown at once and two parts (L) shows the morphology in the case where four tablets are thrown in at one time and is in one part. (M) shows the morphology in the case where one tablet is thrown in at one time and is in one part. (N) shows the morphology in the case where two tablets are thrown in at one time and is in one part. (O) shows the morphology in the case where three tablets are thrown in at one time and is in one part. (A) ) To (O) are continuous packages, which are preferable when the seal packing material opening and charging device shown in FIG. 2 is used. (P)-(U)
Shows an example that is not continuous packaging.

If the continuous package is once set by using the solid processing agent feeding device of a preferred embodiment of the present invention, the solid processing agent is automatically replenished with high precision, and the waste packaging materials can be collectively stored in one place. It will be possible. Furthermore, it was also found that the fact that the packaging is done allows for minimal damage even if the packaging material is torn during transportation.

Example 2 Tablet (IV) was prepared by the following procedure in the production of the color development replenishing tablet for color negative film of Example 1.

Procedure (d) 863 g of carbonate, 31.8 g of potassium hydroxide, 134.5 g of sodium sulfite and 90 g of mannite were pulverized and mixed in a commercial Van Dam mill until the average particle size became 10 μm, and the amount of water added was 40 m.
Granulation was carried out with l. 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. 2 g of sodium N-lauroylalanine is added to the granulated product thus prepared, and mixed for 3 minutes using a mixer in a room whose humidity is controlled to 25 ° C. and 40% RH or less. Then mix the mixture with Kikusui
Using a tableting machine modified from Tough Presto Correct 1527HU manufactured by Co., Ltd., the tablet was compressed into tablets with a filling amount of 2.0 g per tablet to prepare 560 color developing film replenishing tablets (d) for color negative film.

Operation (e) 83 g of hydroxylamine salt, 9.9 g of potassium bromide, 42.9 g of diethylenetriaminepentaacetic acid and 4.6 g of pine flow were crushed and mixed, and the amount of water added was 3.5 ml.
Dry at 30 ° C for 30 minutes to almost completely remove the water content of the granulated product. In this way, 0.3 g of sodium N-lauroylalanine is added to the prepared granulated product, and mixed for 3 minutes using a mixer in a room where the humidity is controlled to 25 ° C. and 40% RH or less. Further, in the same manner as in the operation (d), a tableting machine was used and the filling amount per tablet was 0.5 g, followed by compression tableting to prepare 280 color development replenishing tablets (e) for color negative film.

Operation (f) Developing agent CD-4 [4-amino-3-methyl-N-ethyl-N-β-
(Hydroxy) ethylaniline sulphate] 150 g is ground in a commercial Van Dam mill until the average particle size is 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. 0.3 g of sodium N-lauroylalanine was added to the granules prepared in this way, and the mixture was added at 25 ° C and 40% RH
Mix evenly in a conditioned room for 10 minutes using a mixer. Next, the mixture was compressed into tablets using a tableting machine in the same manner as in step (d) with a filling amount of 0.53 g per tablet, and 280 color development replenishing tablets for color negative film (f). It was created.

Here, 2 tablets (d) and 1 tablet (e) are used.
Tablets and tablets (f) were evaluated as 1 tablet, and a total of 4 tablets were treated as 1-minute packaging solid treatment agents (4), and otherwise the same evaluation as in Example 1 was carried out. However, instead of the solid processing agent residual ratio (%), it was evaluated that how many times all 4 tablets were added by adding 20 times. The results are shown in Table 4.

[0097]

[Table 4]

It can be seen that the effect of the present invention can be satisfactorily achieved even with the tablets classified by part. The reason for the small number of successes is that the tablets do not block due to wrinkles at the packaging material outlet and are not thrown in, and the tablets remain in the package due to the tablets getting caught on the wrinkles of the packaging material.

Example 3 Using the solid processing agent (4) prepared in Example 1, Example 1
Example No. 1-32 packaging material (stretched polypropylene +
Unstretched polypropylene + low density polyethylene)
As shown in Table 6, the filling amount of the color developing replenisher per one package was changed, and a running test was carried out using the automatic developing machine of FIG. 1 and the seal packing material opening and charging device of FIG.

The test is Konica Color Film DD-100.
(Manufactured by Konica Corp.) was treated until the amount of replenishing water became twice as much as the tank liquid.

Fixing is from 2 to 1, stability is from 3 to 2, 2
It was a counter current system from 1 to 1, and the bleaching tank was aerated with an air pump.

Evaporation correction is color development, bleaching, fixing-1, fixing-2, stable-1, stable-2, stable- during temperature control.
10ml, 6.5ml, 7ml, 7ml, 8.6ml, 8.6 in 3 tanks for 1 hour each
Evaporation correction was performed using a program that replenishes water with 9.1 ml and 9.3 ml. When not in operation, the time when not in operation was added up, and the above tanks were collectively replenished with water at the start of operation in the amounts of 7.5 ml, 5 ml, 6 ml, 6 ml, 5 ml, 5 ml and 5 ml per hour.

The tank liquid at the start was prepared by using a replenisher and a starter of the processing agent CNK-4-52 for Konica color negative film.

Other tablets used in the running treatment were prepared as follows.

The amount of replenishing water and the amount of solid processing agent replenishing were as shown in Table 6.

(1) Bleach replenishment tablet operation for color negative film (g) 1,3-Propanediaminetetraacetic acid ferric ammonium monohydrate
190 g, 1,3-propanediaminetetraacetic acid 9 g, and Pine Flow (manufactured by Matsutani Chemical Co., Ltd.) 17 g were pulverized and mixed in the same manner as in the operation (a), and the amount of water added was 8 ml to perform granulation. After the granulation, the granulated product is dried at 60 ° C for 30 minutes to almost completely remove the water content of the granulated product.

Operation (h) 50 g of succinic acid, 83 g of maleic acid, 86 g of potassium bromide and 10.2 g of pine flow are pulverized, mixed and granulated in the same manner as in operation (a). The amount of water added was 17 ml, and after granulation, the granules were dried for 60 minutes at 70 ° C to almost completely remove water.

(2) Fixing replenishing tablet operation for color negative film (k) Ammonium thiosulfate 2500 g, sodium sulfite 180
g, 20 g of potassium carbonate, 20 g of ethylenediamine tetraacetic acid disodium salt and 65 g of Pine Flow (manufactured by Matsutani Chemical Co., Ltd.) are pulverized, mixed and granulated in the same manner as in the operation (a). The amount of water added is 50
After granulation, the granules are dried at 60 ° C for 120 minutes to almost completely remove water from the granules.

Operation (l) The granulated product prepared in the above operation (k) and 13 g of sodium N-lauroylsarcosine are mixed for 3 minutes using a mixer in a room where the humidity is controlled to 25 ° C. and 40% RH or less. . Next, the mixture was compressed into tablets with a tableting machine modified from Tough Pressed Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd. so that the filling amount per tablet was 1.8 g, and 1500 fixing fixer tablets for color negative (1) It was created.

(3) Tablet for stable replenishment for color negative (m) 150 g of m-hydroxybenzaldehyde, 20 g of sodium lauryl sulfate, disodium ethylenediamine tetraacetate 20
g, 16 g of lithium hydroxide monohydrate and 10 g of pine flow are pulverized, mixed and granulated in the same manner as in the operation (a). How much water is added
After granulating to 10 ml, the granulated product is dried at 50 ° C. for 2 hours to almost completely remove the water content of the granulated product.

Operation (n) The granules prepared in the above operation (m) were placed in a room whose humidity was adjusted to 25 ° C. and 40% RH or less, by a tableting machine modified from Kikusui Mfg. Co., Ltd. Tough Press To Collect 1527HU. Compressing tableting was carried out with the filling amount per tablet being 1.41 g to prepare 150 stable replenishment tablets (n) for color negative.

The processing steps are shown below.

[0113]

[Table 5]

The supply of tablets and the amount of water replenishment are shown below.

[0115]

[Table 6]

As a measure of the solubility of the solid processing agent and the accuracy of the amount supplied once, the transmission red density of the imagewise exposed maximum exposed portion of the film after the completion of running was measured. The results are summarized in Table 7.

[0117]

[Table 7]

As is clear from Table 7, the coefficient of friction in the package is 0.
43 and the unit supply amount of the solid processing agent of 0.5 to 50 g is excellent in solubility and color developability (that is, single-time supply accuracy), and particularly 1
It turns out that ~ 20 g is preferred.

If the unit supply amount of the solid processing agent is too large, the solid processing agent is not completely dissolved, the next solid processing agent is charged, and further, such as further charging, the normal circulation is carried out. It does not dissolve to a certain extent, and in short it becomes insoluble.

On the other hand, if the unit supply amount of the solid processing agent is too small, the proportion of the solid processing agent adhering to the packaging material will be large, and the amount will be reduced, resulting in fluctuation of photographic performance. It also causes a high cost of the packaging material.

As another effect, continuous packaging of each sachet (in the present invention, a sachet represents a packaging unit packaged for each unit replenishing and supplying amount of the solid treating agent), whereby the preferable solid treatment of the present invention is achieved. It was found that the solid processing agent can be automatically and accurately replenished once set by using the agent feeding device, and the waste packaging materials can be collectively stored in one place.

It has also been found that the packaging of the package further minimizes damage even if the packaging material is broken during transportation and transportation.

Example 4 Same as Experiment Nos. 1 to 34 of Example 1 except that the developing agent CD-4 of the color development replenishing granule (II) for color negative film prepared in Example 1 was changed to the following compound. I experimented with.
The results are shown below.

[0124]

[Table 8]

[0125]

[Chemical 1]

From Table 8, it can be seen that the compounds of the developing agents (C), (A) and (B) have a preferable solid processing agent residual rate.

Example 5 The solid processing agent (2) was put in the PTP (Pressure Through Package) packaging material of FIG. 12 (a) and stored in the same manner as in Example 1. The coefficient of friction in the package was 0.50.

FIG. 13 relates to a PTP-packed solid processing agent charging device. (A) is a PTP-packed solid processing agent (single processing agent), and (B) is a PTP-packed solid processing agent 13 '. (Multiple processing agents of different types), (C) is a cross-sectional view of the processing agent supply device.

The solid processing agent 13 'packed in PTP is supplied from the side surface of the container, and when the photosensitive material is processed by a certain amount, the information of the processing amount detecting means is sent to the processing agent supply control means.
PT by the turntable 130 connected to the solenoid motor
The P-packaged solid processing agent is pushed into the processing tank by the pushing device 134 breaking the lower part of the PTP package. Then, the packaging material 120 is transported by the transport notch 128 provided on the rotary disk 130.

In addition, the charging device shown in FIG. 2 was replaced with the charging device shown in FIG.
Met.

From this, it was found that the granule treating agent is likely to remain at the contact point 24 'between the upper packaging material and the lower packaging material of the PTP packaging material of FIG. 12 (b). Experiment of Example 1
This is the difference in residual rate from No. 1-23, and the four-sided seal is preferable. Further, since it is opened by pressure, when the solid treatment agent to be added is powder or granules, it is easy to scatter and a four-way seal is preferable.

When the aluminum foil 23 'was replaced with pullulan and the same experiment was carried out, the friction coefficient in the package could not be measured, and the solid processing agent residual rate (%) was 25.8 (%).

From the above, it can be understood that the coefficient of friction in the package has an important meaning even in the case of PTP packaging.

Further, the amount of the unit supply amount was changed once as in the second embodiment. The residual rate was slightly worse than the uniform 4-way seal, but the tendency for the amount was the same. That is, it can be seen that the present invention can be applied to PTP packaging.

Example 6 FIG. 17 is a diagram showing an example of a cartridge type packaging form.

After the storage test as in Example 1, the solid processing agent (3) was used for running in the dulmar dropping device shown in FIG. 14 described in WO92 / 20013. However, the packaging form is as shown in Fig. 17 (packaging material is paper (50μ) solid processing agent (3)
There was a big problem in the input accuracy of. In-pack friction coefficient is
It was impossible to measure.

The causes were the following two points.

That is, in FIG. 14 (a) and FIG. 14 (b), (a) the tablet 32 'to be loaded was stuck in the cartridge and was not in the standby state. Therefore, the tablets 32 'were not actually charged, and therefore the accuracy of charging was poor.

(B) The tablets 31 'and 32' are adhered,
Even if the pushing claw 18 'pushed the tablet 32', the tablet 32 'was difficult to be loaded. After the charging operation many times, it was charged, but a part of the tablet 32 'adhered to the tablet 31', and eventually the amount charged was small,
Therefore, the input accuracy was poor.

[0140] When a double-wrapped product of silica-coated stretched polyethylene terephthalate (12μ) was used on the outside of the above-mentioned packaging material paper (50μ), and a similar experiment was carried out, the coefficient of friction inside the package was 0.42, and the above problem (a) ) Is 100% improved. (B) has been improved by 90%.

The effects of the present invention are better exhibited by the moisture-proof packaged solid processing agent as described above.

Example 7 A running test was carried out using the solid processing agent (2) with the screw feeder type charging device shown in FIG. 15 described in WO92 / 20013.

There was a big problem in the accuracy of the solid processing agent (2), and the causes were the following two points.

15 (a) and 15 (b), (c) In the hopper, due to the adhesiveness of the solid processing agent (2).
There was a space at 34 and the screw couldn't move the correct amount when it was rotated. Therefore, the injection accuracy was poor.

(D) The solid processing agent (2) adhered to the tip portion 33 of the screw, and it should not drop, but it did not drop. Therefore, the charging accuracy was poor.

The table-type feeder feeding device shown in FIG. 16 described in Japanese Patent Laid-Open No. 4-237045 also has the same problem, and there is a big problem in the charging accuracy.

[0147]

The solid processing agent for silver halide photographic light-sensitive materials according to the present invention has a high replenishing amount accuracy, has no danger in transportation and handling, has completed a completely automatic replenishment system, and has many built-in replenishing systems. It is possible to use a compact automatic processor without the replenishment tank.

Also, the need for storing liquid replenisher is eliminated, the process stability is excellent, the amount of chemical waste liquid can be reduced, the use of plastic bottles for liquids is eliminated, and the plastic packaging materials are reduced. The system can be achieved.

[Brief description of drawings]

FIG. 1 is a cross-sectional view of a processing agent charging section and a processing agent charging device of an automatic processor.

FIG. 2 is a perspective view showing an example of a seal packaging material opening and charging device.

FIG. 3 is a perspective view of the seal packing material opening and charging device seen from another angle.

FIG. 4 is an explanatory diagram of an example in which the feed rate is different.

FIG. 5 is an explanatory diagram of an embodiment including reverse rotation.

FIG. 6 is an explanatory diagram of an embodiment in which the phase is changed.

FIG. 7 is a flowchart of control.

FIG. 8 is a diagram showing an example of seal packaging and stick packaging.

FIG. 9 is a plan view showing a specific example of seal packaging.

FIG. 10 is a state diagram showing an example in which the solid processing agent sealed and packaged is contained in a container.

FIG. 11 is a plan view showing a specific example of continuous seal packaging.

FIG. 12 is a cross-sectional view showing a specific example of PTP packaging.

FIG. 13 is a cross-sectional view and a perspective view of a PTP packaging treatment agent supply device.

FIG. 14 is a cross-sectional view showing an example of a charging unit of the dharma dropping charging device.

FIG. 15 is a sectional view showing an example of a screw feeder type charging device.

FIG. 16 is a perspective view showing an example of a powdery processing agent supply device for each part.

FIG. 17 is a perspective view showing an example of a cartridge type packaging form.

[Explanation of symbols]

 1 Processing Tank 2 Constant Temperature Tank 3 Sealing Packing Material Opening Feeding Device 4 Feeding Part 5 Enclosure 6 Storage Container 7 Lid 8 First Transfer Means 9 Second Transfer Means 10 Cutter 11 Cutter Tip 12 Guide 13 Input Port 14 Detection Means 15 Covered Detection unit 16 Processing amount supply control means 18 Gear 19 Drive source H Processing agent package T Solid processing agent 13 'Tablet (solid processing agent) 17' Processing agent supply means 18 'Push claw 22' PET 23 'Aluminum foil 24' Upper part Location of contact point between packaging material and lower packaging material 31 'Tablet (solid processing agent) 32' Tablet (solid processing agent) 33 Screw tip 34 Space

Claims (2)

[Claims] 1. A solid processing agent package for a silver halide photographic light-sensitive material, wherein the solid processing agent is 0.
Pre-divided and weighed in the range of 5 to 50 g, containing at least a para-phenylenediamine derivative, and the outside of the solid processing agent is a packaging material having an internal friction coefficient between the solid processing agent surface and the packaging material surface of 1.5 or less. A solid processing agent package for a silver halide photographic light-sensitive material, which is packaged. 2. The solid processing agent package for a silver halide photographic light-sensitive material according to claim 1, wherein the packaging agent is a granule or a tablet.