JPH08146566A - Manufacture of solid processing agent for silver halide photosensitive material - Google Patents

Abstract

PURPOSE: To reduce the dispersion of production without impairing the yield at the production level by wet-granulating a powder raw material containing a water-soluble binder, and drying the obtained granulated material at a specific temperature with a fluidized bed. CONSTITUTION: A powder raw material containing a water-soluble binder having the melting point of 40-80 deg.C is wet-granulated, and the obtained granulated material is dried at the temperature of the melting point or above of the water- soluble binder and 80 deg.C or below with a fluidized bed for 5-240min. Grains are rectified after drying is completed, and the drying temperature is set lower by 10 deg.C or above than the melting point of the water-soluble binder before the drying process is completed. The powder raw material contains sugar alcohols, the powder raw material contains the carbonate of an alkaline metal, and the powder raw material contains the water-soluble binder of 2-15wt.% having the melting point of 45-80 deg.C. A solid processing agent obtained by this manufacture is compressed and molded, and polyethylene glycol having the molecular weight of 3000-20000 is used for the water-soluble binder having the melting point of 45-80 deg.C.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a solid processing agent for a silver halide photographic light-sensitive material, and more specifically, a silver halide having improved handling properties during production, less variation in quality, and no problem in distribution. The present invention relates to a method for producing a solid processing agent for a photographic light-sensitive material.

[0002]

2. Description of the Related Art In recent years, solidification of a processing agent for silver halide photographic light-sensitive materials has been studied from the viewpoints of consideration for the environment and handleability on the user side. However, since the processing agent for silver halide photographic light-sensitive material also contains harmful components to the human body, it is necessary to take sufficient care not to generate and disperse fine powder during solidification. In addition, such fine particle components have poor handling properties during formulation work,
This is a big problem because it impairs the production yield.

Japanese Patent Laid-Open No. 4-254853 describes that a treatment agent component is granulated by using a water-soluble binder such as polyethylene glycol to reduce fine particles and improve the handling property of a solid treatment agent. ing. Certainly, according to this technique, although the fine particles are reduced, there remains a problem in productivity such as product yield and variation, and particularly when the obtained granules are compression-molded into a tablet-type solid processing agent, it is desirable. There was a problem that the hardness could not be obtained or the tablet expanded when stored at high temperature.

Japanese Patent Laid-Open No. 5-119454 and European Patent No. 595,312
JP-A No. 2003-242242 discloses a method of obtaining a tablet-type treatment agent by granulating after compression using a water-soluble binder, but it deals with the amount charged at the laboratory level, and the production level is taken into consideration. However, the problem of high temperature storage cannot be solved.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and firstly, the object of the present invention is to minimize the variation of production without impairing the yield at the production level. A second object is to provide a method for producing a solid processing agent for a silver halide photographic light-sensitive material, and secondly, a solid processing for a silver halide photographic light-sensitive material, which does not cause a problem of expansion due to high temperature storage even when compressed into tablets. It is to provide a manufacturing method of the agent.

[0006]

The above object of the present invention is to wet granulate a powder raw material containing a water-soluble binder having a melting point of 40 ° C. or higher and 80 ° C. or lower, and obtain the obtained granulated product. 5. A method for producing a solid processing agent for a silver halide photographic light-sensitive material, which comprises drying in a fluidized bed at a temperature above the melting point of the water-soluble binder and below 80 ° C.
Minutes, 240 minutes or less, after drying, after drying,
Perform sizing, make the drying temperature 10 ° C or more lower than the melting point of the water-soluble binder before the end of the drying step, make the powder raw material contain sugar alcohol, and make the powder raw material an alkali metal carbonate. Containing a melting point of 45 ° C. or higher in the powder raw material,
Contain 2% by weight or more and 15% by weight or less of a water-soluble binder having a temperature of 80 ° C or less, compression-mold the solid processing agent obtained by these production methods, and have a melting point of 45 ° C or more and 80 ° C or less. The binder is polyethylene glycol having a molecular weight of 3,000 to 20,000.

The present invention will be described in detail below.

The manufacturing method of the present invention has a melting point of 40.degree.
It is applied when a powder containing a water-soluble binder having a temperature of not higher than 0 ° C. is granulated into a solid processing agent for a silver halide photographic light-sensitive material.

As the water-soluble binder having a melting point of 40 ° C. or higher and 80 ° C. or lower, polyethylene glycol, polyoxyethylene alkyl ether, polyoxyethylene alkylaryl ether, polyoxyethylene polyoxyalkylene block copolymer, polyoxyethylene alkyl Examples thereof include esters and polyoxyethylene alkylamides, and among them, polyethylene glycol has a molecular weight of 3,
Those of 000 to 20,000 are preferable from the viewpoint of processability of the photographic processing agent. The addition amount is 2% by weight with respect to the solid processing agent.
As described above, it is preferably 15% by weight or less. When it is 2% by weight or less, the fine particle component is increased, the loss is increased during the drying process, and the variation in productivity is increased. Also, 15% by weight
In the above case, a large amount of aggregates are generated during the granulation process or the drying process, and workability is greatly impaired. It is more preferably 4% by weight or more and 10% by weight or less.

The solid processing agent obtained according to the present invention contains sugar alcohols in an amount of 2% by weight or more and 20% by weight or less, so that the reduction of fine particles, the reduction of the variation in productivity and the compression molding into tablets. It is preferable from the viewpoint of improving hardness. Here, the sugar alcohol is a compound in which an aldehyde group and a ketone group of sugar are reduced to form a first alcohol group and a second alcohol group, respectively, and specific exemplified compounds are shown below.

A-1 glycerin A-2 D-trait A-3 L-trait A-4 meso-erythret A-5 D-arabit A-6 L-arabit A-7 Adnit A-8 xylit A-9 D- Sorbit A-10 L-Sorbit A-11 D-Mannit A-12 L-Mannit A-13 D-Igit A-14 L-Igit A-15 D-Talit A-16 L-Talit A-17 Zulsit A -18 Among the allozulcit, preferred in the present invention are A-11 and A-9.
Is.

When the solid treating agent obtained by the present invention contains an alkali metal carbonate such as potassium carbonate or sodium carbonate, the effect of the present invention can be remarkably obtained.

In the present invention, the powder raw material may be used as it is, without being pulverized, but it is preferable to weigh the pulverized material, and then carry out the steps of granulating and drying.

The method of granulating into granules may be any so-called wet granulation using a solvent, preferably rolling granulation,
Extrusion granulation, stirring granulation, fluidized bed granulation, and crushing granulation. The solvents used are methyl alcohol, ethyl alcohol, propylene alcohol, isopropyl alcohol,
Alcohols such as butyl alcohol, water or a combination solvent thereof is preferable, and water is particularly preferable in view of influence on photographic processing performance and safety.

It is essential that the granules obtained by the granulation are subjected to a drying step and sufficiently dried, and the drying device is provided with a means for forcibly flowing the granules such as a fluidized bed drying device. Those used in the present invention.

In the present invention, the granules are dried at a temperature of not lower than the melting point of the water-soluble binder having a melting point of 40 ° C. to 80 ° C. and not higher than 80 ° C. By drying at a temperature not lower than the melting point of the water-soluble binder and not higher than 80 ° C., it is possible to make the fine particle component almost nonexistent, and the variation between production lots is significantly reduced even at the actual production level. Drying is performed at this temperature for about 5 to 240 minutes. If the time is less than 5 minutes, the effect of the present invention is not sufficiently exhibited, and if the time is more than 240 minutes, a large amount of aggregates of granules are generated on the wall surface of the drying device, or the compound of the granules is oxidized, which is preferable. Absent. Also, drying at a temperature over 80 ° C is not preferable because it causes problems such as decomposition and oxidation of the material.

The period during which the drying temperature is set to a temperature not lower than the melting point of the water-soluble binder and not higher than 80 ° C. may be the entire period of the drying step,
Although it may be a part of the step, in order to remove the agglomerated granules on the wall surface of the drying device, it is preferable that the drying temperature is 10 ° C. or more lower than the melting point of the water-soluble binder contained immediately before the end of the drying step. .

The end point of the drying is confirmed by sampling the sample during the drying and determining the end point when the water content becomes 0.01 to 1.5% by weight. Here, the water content means a value obtained by subtracting the water content of the powder before granulation from the water content calculated by measuring the water content of the granules with a moisture meter, that is, the remaining amount of water added during granulation. . At this time, the amount of water of crystallization previously contained in the powder raw material is not included.

It is preferable to include a sizing step during or after drying. The sizing step is used for the purpose of improving the drying efficiency of the granulated granules and adjusting the particle size distribution of the particles. The sizing apparatus is composed of a means for crushing the granules and a means for classifying by means of a screen, and the granules are crushed to a particle size which passes through the screen. A commercially available coating mill, Fitz mill, tornado mill, flash mill or the like can be used as the particle size control device.

Next, the tablet manufacturing method will be described.

In the present invention, the tablet means a solid processing agent in which at least a part of the raw material is granules, which is compression-molded into a certain shape. In order to exert the effect of the present invention, the tablet is molded only from the granules. Is preferred. Furthermore,
The granules are preferably formed of one type of granules, but may be formed of two or more types in order to obtain storage stability. Two
When more than one type of granules are mixed and compression molded, or a lubricant is mixed, it is preferable to mix them for about 5 to 10 minutes by using an ordinary mixer. The lubricant to be mixed is preferably a water-soluble surfactant because the tablet is a photographic processing agent.

The tablet-like solid processing agent can be produced by using a compressor such as a hydraulic press, a single-shot tableting machine, a rotary tableting machine and a briquetting machine. Among them, the rotary tableting machine is used in large quantities. It is advantageous in terms of productivity.

In the rotary tableting machine, the upper punch and the lower punch are aligned in a cylindrical shape by a turntable, and when the granules are filled by the hopper, the upper punch and the lower punch are pressed and compressed,
Tablets can be made continuously. The step of compressing the granules into tablets is the first step in which the upper and lower punches are compressed while approaching each other along the pressure roller, and the upper and lower punches move horizontally along the lowermost end and the uppermost end of the pressure roller, respectively. It consists of a second step and a third step of completing and releasing the compression. The time required for the first process is called the dynamic compression time, the time required for the second process is called the compression stagnation time, and both are called the total compression time. Here, if the rotation speed of the turntable becomes faster, the compression stagnation time becomes shorter, and the pressure strain inside the tablet may not be sufficiently relieved, and the tablet may expand over time. Depending on the physical properties of the granules, the performance to be imparted to the tablets, the tableting main pressure, the tableting preload, the compression stagnation time, the rotation speed of the turntable, and the filling amount are set, but in the present invention, problems such as capping and lamination are set. It is preferable to carry out in the following range.

A preferred range Particularly preferable range tabletting the pressure 140~4300Kg / cm ² 700~2100Kg / cm ² strokes tablet preload ^{1.4~ 280Kg / cm 2 14~ 140Kg /} cm 2 compression dwell time from 0.02 to 0.60 seconds from 0.03 to 0.12 seconds Rotational speed of turntable 1-30 rpm 5-20 rpm Filling amount 1-30 g 5-15 g Also, the shape of the tablet is arbitrary, but from the viewpoint of handling, a cylindrical shape is preferable, and its diameter is a tablet. However, in the present invention, the range of 10 to 35 mm is preferable.

The environmental conditions at the time of tableting are 20 from the viewpoint of moisture absorption and the like.
~ 26 ℃, 40% RH or less is desirable.

[0026]

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 (Operation 1) 60.0 Kg of potassium carbonate, 8.5 Kg of sodium carbonate
In addition, 4.0Kg of the additives listed in Table 1 were used in a room where the temperature and humidity were adjusted to 30 ° C and 50% RH or less, and Okada Seiko Co., Ltd. New Speed
Using Kneader NSK-750SJ, water was added and the mixture was kneaded for 7 minutes. Addition of water at the time of granulation should be 3
It was carried out by dropping at a rate of 750 ml / min at a weight percentage.

The granulated product was dried under the conditions shown in Table 1 by using a fluidized bed dryer Slitflow FB-15 manufactured by Okawara Seisakusho Co., Ltd. to prepare each granule. The above-described series of operations was set as the first batch, and each experimental sample was similarly repeated until the fifth batch.

The following evaluation was performed on the obtained granules.

<Particle generation rate> 40 g of granules were sampled for each batch and shaken with a commercially available sieve shaking material for 5 minutes to obtain 100
The amount (g) of fine particles that passed through the mesh (JIS standard) was measured, and the average value of the particle generation rates (= fine particle amount / 40 g × 100) of the first to fifth batches was obtained. The evaluation criteria are shown below.

5: 0% ≤ average particle generation rate ≤ 1.5% 4: 1.5% <average particle generation rate ≤ 3.0% 3: 3.0% <average particle generation rate ≤ 5.0% 2: 5.0% < Average value of fine particle generation rate ≦ 8.0% 1: 8.0% <Average value of fine particle generation rate << Batch variation >> The relative standard deviation of the fine particle generation rate of the first to fifth batches of each sample was determined.

(Evaluation Criteria) 5: 0% ≦ relative standard deviation ≦ 10% 4: 10% <relative standard deviation ≦ 20% 3: 20% <relative standard deviation ≦ 30% 2: 40% <relative standard deviation ≦ 60 % 1: 60% <Relative standard deviation << Observation of granule sample after storage >> The granule sample was observed after being stored in a room whose temperature and humidity were adjusted to 25 ° C and 40% RH.

(Evaluation Criteria) A: No particular change B: Agglomerates are partially generated. X: Agglomerates are largely generated. The above results are shown in Table 1.

[0034]

[Table 1]

As is clear from this, the melting point is 40-80.
At the time of wet granulating and drying the powder raw material containing the water-soluble binder at 0 ° C, by causing the powder to flow at a temperature of not lower than the melting point of the binder and not higher than 80 ° C and drying, the generation of fine particles is small,
It can be seen that it is possible to provide a granular solid processing agent with little variation between batches and having no deterioration even when stored.

Example 2 In Experiment No. 1-3 of Example 1, each granule was prepared in the same manner as in Example 1 except that the drying conditions were changed as shown in Table 3. The drying conditions shown in the table are shown below.

A: Dry at 50 ° C. for 3 hours B: Dry at 65 ° C. for 3 hours C: Dry at 50 ° C. for 3 hours, then at 65 ° C. for 3 minutes D: Dry at 50 ° C. for 3 hours, then at 65 ° C. for 6 minutes Drying E: Drying at 50 ° C for 3 hours, drying at 65 ° C for 15 minutes F: Drying at 50 ° C for 3 hours, drying at 65 ° C for 60 minutes G: Drying at 50 ° C for 3 hours, drying at 65 ° C for 180 minutes H : Dry at 50 ° C for 3 hours, then at 65 ° C for 240 minutes I: Dry at 50 ° C for 3 hours, then at 65 ° C for 360 minutes J: Dry at 65 ° C for 3 hours, then at 45 ° C for 30 minutes For the granule sample, the particle generation rate and the variation between batches were evaluated in the same manner, and the state of adhesion of the granules to the inner wall of the drying device at the end of drying was observed.

<< Adhesion of Granules to Inner Wall of Device >>: Almost no adhesion. Δ: There is an adhering substance, but it can be easily removed. ×: A large amount of adhering substance takes time to remove.

[0039]

[Table 2]

As a result, the melting point of the water-soluble binder is 80 ° C. or higher.
The drying time at the following temperature is preferably 5 to 240 minutes, more preferably 15 to 180 minutes, and by making the drying temperature 10 ° C or more lower than the melting point of the water-soluble binder immediately before the end of drying,
It can be seen that the adhesion of the granules to the inner wall of the dryer is reduced and the handleability is improved.

Example 3 Granules were prepared in the same manner as in Example 1 except that the kinds and amounts of additives were changed as shown in Table 3, and the rate of generation of fine particles, the variation between batches and the inner wall of the apparatus were measured. Table 3 shows the results of the evaluation of the adhesion of the granules.

[0042]

[Table 3]

Accordingly, the amount of the water-soluble binder added is 2 to
It is understood that 20% by weight is preferable, and the effect of the present invention is further exerted at 4 to 10% by weight. Further, it can be seen that the effect of the present invention is enhanced by the combined use of sugar alcohols such as D-mannite.

Example 4 In (Operation 1) of Example 1, after completion of drying, a New Speed Mill manufactured by Okada Seiko Co., Ltd. was used to carry out sizing using a 1.0 mm screen to prepare each granule. Table 4 shows the results of the same experiments and evaluations as in Example 1 except for the above.

[0045]

[Table 4]

From this, it can be seen that the effect of the present invention is more remarkably exhibited when the particle size is adjusted after drying.

Example 5 A tablet-type solid processing agent for color development was prepared by the following procedure.

(Operation 2) Potassium Carbonate 40.0 Kg Sodium Sulfite 6.4 Kg Additive 3 (Listed in Table 5) Additive Amount Listed in Table Additive 4 (Listed in Table 5) 4.0 Kg Diethylenetriamine 5 Sodium Acetate 5 Sodium 2.4 Kg Paratoluene Sodium sulfonate 8.0 kg The above compositions were granulated and dried by the same operation as in Example 1 under the drying conditions shown in Table 5. Next, the granules were sized in the same manner as in Example 4 to prepare granules for alkaline agents.

(Operation 3) Hydroxylamine Sulfate 40.0 Kg Potassium Bromide 4.0 Kg Pyrocatechol-3,5-disulfonic acid disodium monohydrate 2.0 Kg Maltodextrin 4.0 Kg The above composition was granulated in the same manner as in Example 1. Then, after drying in a fluidized bed at 50 ° C. for 3 hours, the granules were sized in the same manner as in Example 4 to prepare granules for preservatives.

(Operation 4) 4-amino-3-methyl-N-ethyl-
Granules of β- (hydroxy) ethylaniline sulfate (CD-4) (manufactured by Konica Chemical Co., Ltd.) were sized in the same manner as in Example 4 to prepare granules for color developing agent.

(Operation 5) Granules produced in Operation 2 60Kg Granules produced in Operation 3 10g Granules produced in Operation 4 10g Myristoyl-N-methyl-β-alanine sodium 0.4Kg (particle size 100 μm The granulated product prepared in steps 2 to 4 is separated and mixed with the above composition by a cross rotary type mixer for 10 minutes, and then using a Kikusui Seisakusho 2028HUS-AWC tableting machine. Tableted. Tableting conditions are 27 cylindrical punches, main pressure 1400 kg / cm ² , preload 1
40 kg / cm ^3, the rotational speed of the turntable 10 rpm, the compression dwell time 0.05 sec, is set to charge 11.60 g. The prepared color developing tablet was a cylindrical type having a diameter of 30 mm and a thickness of about 10 mm.

The following evaluation was performed on the obtained tablet-type solid processing agent.

<< Tablet Hardness >> 30 tablets of each tablet sample were taken, the hardness was measured using a speed checker TS-50N manufactured by Okada Seiko Co., Ltd., and an average value and a relative standard deviation were obtained.

<< Tablet Expansion >> Each tablet sample was tested at 25 ° C and 48% RH.
After storage in a temperature-controlled and humidity-controlled room until the amount of moisture absorption reached 500 mg, it was filled in a barrier package (made of aluminum) and stored in a constant temperature bath at 50 ° C for 1 week. The diameter of each tablet sample after storage was measured and evaluated for swelling.

⊚: Tablet diameter = 30 mm to 31 mm ◯: Tablet diameter = 31 mm to 32 mm Δ: Tablet diameter = 33 mm to 34 mm ×: Tablet diameter = 35 mm or more Table 5 shows the above evaluation results.

[0056]

[Table 5]

The following can be understood from the results of Table 5.

Granules containing granules for alkaline agents obtained by drying a granule containing a water-soluble binder having a melting point of 40 to 80 ° C. in a fluidized bed at a temperature higher than the melting point of the water-soluble binder. The tablet obtained from the product has almost no swelling due to storage, has a large hardness, and can greatly improve the variation in hardness. The effect is further enhanced by the combined use with sugar alcohols such as D-mannite. The effect of the present invention is remarkable when the amount of the water-soluble binder in the granule for agent is 1% by weight or more and 20% by weight or less (particularly 4% by weight to 10% by weight).

Example 6 (Experiment No. 5-1 of Example 5, 5-4, 5-7, except that the drying conditions of the alkaline agent granulated product was changed to 85 ° C. for 3 hours. When an alkaline agent granulated product was prepared in the same manner as in the operation 2), the quality (coloring) was extremely deteriorated and the product had no commercial value.

[0060]

Industrial Applicability According to the present invention, it is possible to obtain a granulated product which has a small amount of fine particle components, a small variation between lots and a good storability, and therefore is suitable for producing tablets by compression molding. Tablets also have excellent hardness and almost no deformation.

Claims (9)

[Claims] 1. A powder raw material containing a water-soluble binder having a melting point of 40 ° C. or higher and 80 ° C. or lower is wet-granulated, and the obtained granulated product is fluidized bed to have a melting point of the water-soluble binder or higher. A method for producing a solid processing agent for a silver halide photographic light-sensitive material, which comprises drying at a temperature of 80 ° C. or lower. 2. The method for producing a solid processing agent for a silver halide photographic light-sensitive material according to claim 1, wherein the drying is carried out for 5 minutes or more and 240 minutes or less. 3. The method for producing a solid processing agent for a silver halide photographic light-sensitive material according to claim 1, wherein sizing is performed after completion of drying. 4. The solid processing for silver halide photographic light-sensitive materials according to claim 1, 2 or 3, wherein the drying temperature is 10 ° C. or more lower than the melting point of the water-soluble binder before the completion of the drying step. Method of manufacturing agent. 5. The method for producing a solid processing agent for a silver halide photographic light-sensitive material according to claim 1, 2, 3 or 4, wherein the powder raw material contains a sugar alcohol. 6. The method for producing a solid processing agent for a silver halide photographic light-sensitive material according to claim 1, wherein the powder raw material contains an alkali metal carbonate. 7. The powder raw material contains a water-soluble binder having a melting point of 45 ° C. or more and 80 ° C. or less in an amount of 2% by weight or more and 15% by weight or less, 1, 2, 3, 7. The method for producing a solid processing agent for silver halide photographic light-sensitive material as described in 4, 5, or 6. 8. A method for producing a solid processing agent for a silver halide photographic light-sensitive material, which comprises compression-molding the solid processing agent obtained by the method according to any one of claims 1 to 7. 9. The water-soluble binder having a melting point of 45 ° C. or higher and 80 ° C. or lower is polyethylene glycol having a molecular weight of 3,000 to 20,000, which is characterized in that the water-soluble binder is 1, 2, 3, 4, 5, 6, 7.
Or the method for producing a solid processing agent for a silver halide photographic light-sensitive material as described in 8 above.