JPH08146569A - Manufacture of solid processing agent for silver halide photosensitive material - Google Patents

Abstract

PURPOSE: To properly mass-produce a tablet-like solid processing agent for the color development of a silver halide photosensitive material containing carbonate. CONSTITUTION: A powdery and granular material at least partially granulated and containing a paraphenylenediamine color developing agent and carbonate is filled in a mortar and compressed with a rod for compression molding in a continuous tableting machine. The difference between the temperature of the powdery and granular material and the temperature of the rod and mortar at the starting time of compression molding is set to 10 deg.C or below to manufacture a tablet-like solid processing agent for a silver halide photosensitive material. The percentage content of carbonate in the tablet-like solid processing agent is set to 25wt.% or above, the absolute moisture quantity is set to 0.0080kg H2 O/kg air or below as the environmental condition at the time of compression molding, the compression stagnation time is set to 0.004sec or above for compression molding, and the filling depth of the powdery and granular material into the mortar is set to 5mm or above for compression molding.

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 tablet-like solid processing agent for a silver halide photographic light-sensitive material, and more specifically, at least a part of a powder raw material for a color developing agent containing carbonate as a buffering agent is granulated. The present invention relates to a method for producing a tablet-like solid processing agent for silver halide photographic light-sensitive materials, which is excellent in mass productivity when granulated and compressed into tablets by a continuous tableting machine.

[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 viewpoint of consideration for the environment and handleability on the user side, and tablet-shaped solid processing agents have been put into practical use. Such tablet-like solid processing agent can be produced by using a compressor such as a continuous hydraulic press machine, a continuous single-shot tableting machine, a rotary tableting machine or a continuous briquetting machine. Type tablet press, or
It is advantageous in terms of mass productivity to use a continuous single-shot tableting machine (preferably a double-stroke system such as Masina DC manufactured by Masina Co., Ltd.).

In a rotary tableting machine whose mechanism is shown in FIG. 1, an upper punch 3 and a lower punch 4 are aligned in a cylindrical shape by a turntable 5, and when a powder raw material is filled by a hopper 7, the upper punch is pressed. 3 and the lower punch 4 are pressed and compressed to continuously produce tablets.

The pressurizing system of the continuous type single-punch tableting machine includes a hydraulic system and an exene pressurizing system utilizing the flywheel effect.
It is preferable when tableting a powder or granule having poor moldability.

[0005]

However, a carbonate may be used as a buffer in a color developing solution containing a paraphenylenediamine type color developing agent, and a raw material powder for a developer composed of such a component may be used. When granulating at least a part of the body into granules and then compression-molding into tablets with a continuous tableting machine, when attempting continuous tableting, the powder adheres to the punch from a relatively early stage, and It turned out that there is a tendency that the advantages of the mass productivity of the tabletting machine cannot be exhibited.

Further, due to the sticking to the punch, the hardness and abrasion resistance of the tablets are deteriorated, and the weight of each tablet varies, which causes a serious problem in terms of performance as a photographic processing tablet.

The present invention has been made under the above circumstances, and an object thereof is to provide a production method suitable for stable mass production of a tablet-like solid processing agent for color development of a silver halide photographic light-sensitive material containing a carbonate. To do.

[0008]

Means for Solving the Problems The above-mentioned object of the present invention is to fill a powder with a granular material containing a para-phenylenediamine color developing agent and a carbonate in a die, at least a part of which is a granulated material. Then, in compression molding with a continuous tableting machine that compresses with a pestle, the difference between the temperature of the powder and granules at the start of compression molding and the temperature of the pestle and die is 10 ° C or less. For manufacturing tablet solid processing agent for tablets, the carbonate content of tablet solid processing agent is 25% by weight or more, and the environmental conditions during compression molding are absolute water content of 0.0080 kg H ₂ O / kg air or less. That is, the compression stagnation time is 0.004 seconds or more and the molding is performed, and the depth of the powder or granular material packed in the die is 5 mm or more.

That is, the present inventor has found that the raw material granules including those granulated into granules have a temperature higher than the normal ambient temperature except when the granules heated during granulation are sufficiently cooled. Moisture around the granules at high temperature is condensed on the surface of the pestle and die at a temperature almost equal to the ambient temperature to dissolve (deliquesce) carbonates that have low critical relative humidity and are easily dissolved. Considering that it causes adhesion of granules to the punch, we examined the allowable temperature range of the raw material granules and found that the temperature difference between the punch and die at the start of compression molding was 10 ° C or less. It was the invention. Naturally, it is preferable that the humidity is one of the environmental conditions at the time of compression molding, and the absolute water content is 0.0080 kg H ₂ O / kg air or less, and the effect of the present invention is great.
Further, as the depth of the granular material packed into the mortar is as deep as 5 mm or more, the weight variation becomes large. However, the present invention can suppress the weight variation even if the filling depth is large.

The present invention will be described in detail below.

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. From the viewpoint of processing agent performance and handleability, 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 for compression molding or a lubricant is mixed, it is preferable to mix them for about 3 to 30 minutes using an ordinary mixer. The lubricant to be mixed is preferably a water-soluble surfactant because the tablet is a photographic processing agent.

Usually when the color developing agent contains a carbonate,
The content thereof is about 10 to 80% by weight, but particularly in a color developing agent system in which 25% by weight or more of the powder particles to be compression-molded are carbonates, the production method of the present invention unfailingly exhibits effects. To do.

The step of compressing the granules into tablets by the rotary tableting machine is the first step in which the upper and lower punches 3 and 4 are compressed along the pressure rollers 1 and 2 while approaching each other.
It comprises a second process in which the upper and lower punches move horizontally along the lowermost and uppermost ends of the pressure roller, and a third process in which compression is completed and discharged. The process of compressing granules into tablets with a continuous single-shot tableting machine is the first process in which the upper punch is lowered by the ram cylinder while the upper and lower punches are close to each other, and the first and second punches are compressed with a constant pressure. 2 processes,
Completing the compression, the upper punch rises and consists of the third step of releasing the tablet. 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 5 becomes faster, or if the cycle of the upper punch moving down and stopping becomes faster, the production amount increases, but the compression stagnation time becomes shorter, and the pressure distortion inside the tablet is sufficiently relaxed. Instead, the tablets may expand over time. The hardness of the tablet,
The abrasion resistance is improved. The physical properties of the granules, the tableting main pressure, the compression stagnation time, and the filling amount are set according to the performance to be imparted to the tablet, but in the present invention, within the range shown below so that problems such as capping and lamination do not occur. It is preferably carried out.

Preferred range Particularly preferred range Tableting main pressure 140 to 4300 kg / cm ² 700 to 2100 kg / cm ² Compression stagnation time 0.004 to 1.00 seconds 0.05 to 0.80 seconds Filling amount 1 to 30 g 5 to 15 g Further, tablet shape Although it is arbitrary, a cylindrical shape is preferable from the viewpoint of handling in production, and its diameter is arbitrary depending on the purpose of use of the tablet, but in the present invention, the range is preferably 10 to 35 mm.

Preferred carbonates used in the color developing agent are potassium carbonate and sodium carbonate.

As the para-phenylenediamine compound, a compound having a water-soluble group is preferable. Examples of the para-phenylenediamine-based compound having a water-soluble group include those having at least one water-soluble group in the amino group of the para-phenylenediamine-based compound or on the benzene nucleus. It is O and the specific water-soluble _{group, - (CH 2) n CH} 2 OH, -
(CH ₂ ) _m NHSO ₂ (CH ₂ ) _n CH ₃ , − (CH ₂ ) _m O (CH ₂ ) _n CH ₃ , − (CH ₂ CH
₂ O) _n C _m H _{2m + 1} , —COOH group, —SO ₃ H group (m and n are respectively
Represents an integer of 0 or more. ) Etc. are mentioned as a preferable thing. Specific examples of the para-phenylenediamine compounds preferably used include (C-1) to (C-16) and the same compounds described in JP-A No. 4-86741, pages 7 to 9.
No. 3-246543, pages 6-10 (1)-(26)
Etc. The color developing agent is usually used in the form of hydrochloride, sulfate, p-toluenesulfonate, or the like. The compounds preferably used are shown below.

[0017]

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[0018]

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[0019]

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[0020]

[Chemical 4]

Among these, particularly preferable ones are (C-1), (C-3), (C-17) to (C-2).
0), and more preferred are (C-1) and (C-
3).

The tablet-like solid processing agent obtained by the present invention preferably contains sugar alcohols in an amount of 2% by weight or more and 20% by weight or less 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 Among the -18 allozulcit, the preferred ones are A-11 and A-9.

As a method for granulating granules, rolling granulation, extrusion granulation, stirring granulation, fluidized bed granulation and crush granulation can be preferably used. The solvent used for granulation is preferably alcohols such as methyl alcohol, ethyl alcohol, propylene alcohol, isopropyl alcohol, butyl alcohol, etc., water or a solvent in combination thereof, and considering the influence on photographic processing performance and safety. , Especially water is preferred. The solvent may be used alone, but preferably contains a binder and the like. The binder has a function of binding powders and granules, and for reasons such as solubility and photosensitive material processing performance, sugars, water-soluble polymers, etc., specifically sugar alcohols, monosaccharides, disaccharides, dextrins. , Celluloses,
Polyalkylene glycols and polyvinylpyrrolidones are preferable, and dextrins and polyalkylene glycols are particularly preferable. Further, an oxidizing agent, a reducing agent, an alkaline agent, a buffer agent, etc. may be added to the extent that the effects of the present invention are not impaired. The granules obtained by the granulation are subjected to a drying step and sufficiently dried.

[0025]

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

(Operation 1) Potassium carbonate 37.5 kg Sodium sulfite 5.83 kg Sugar alcohol 4.0 kg Polyethylene glycol (Nippon Oil & Fats Co., Ltd. PEG # 6000) 5.2 kg Diethylenetriamine pentaacetic acid 5 sodium 2.4 kg Sodium paratoluenesulfonate 8.0 kg Each of the above New Speed Kneader NSK-750SJ manufactured by Okada Seiko Co., Ltd. in a room where the composition is temperature-controlled and humidity-controlled at 30 ° C. and 50% RH or less.
Was added, and the mixture was granulated and kneaded for 7 minutes. Addition of water at the time of granulation is 750 ml / m at 3% by weight of the total amount charged at the beginning of granulation.
Dropping was performed at a rate of in.

The granulated product was subjected to fluidized drying at 60 ° C. for 5 hours using a fluidized bed dryer Slitflow FB-15 manufactured by Okawara Seisakusho, and after completion of the drying, New Speed Mill manufactured by Okada Seiko Co., Ltd.
Then, the granules were sized using a 1.0 mm screen to prepare granules for alkaline agents.

(Operation 2) Hydroxylamine sulfate 36.0 kg Potassium bromide 4.3 kg Pyrocatechol-3,5-disulfonic acid disodium monohydrate 2.0 kg Pine flow (manufactured by Matsutani Chemical Co., Ltd.) 2.8 kg The above composition (Operation 1) Granulate in the same manner as above, dry in a fluidized bed at 50 ° C. for 3 hours, and then perform granulation in the same manner
A granule for preservative was prepared.

(Operation 3) 4-amino-3-methyl-N-ethyl-
β- (hydroxy) ethylaniline sulfate (CD-4)
(Merck) 65 kg, disulfoethylhydroxylamine disodium 20 kg and mannite 8.5 kg (operation 1)
After granulating in the same manner as above and drying in a fluidized bed at 45 ° C. for 4 hours, granulation was performed in the same manner to prepare a granulated product for a color developing agent.

(Operation 4) Granules created in Operation 1 62.93 kg Granules created in Operation 2 4.51 kg Granules created in Operation 3 9.35 kg Myristoyl-N-methyl-β-alanine sodium 0.27 kg ( Granules pulverized to a particle size of 100 μm or less) The granules created in steps 1 to 3 are separated and mixed with the above composition for 10 minutes with a cross rotary mixer, and then the Kikusui Seisakusho 2028HUS-AWC tablet press. Were compressed using. Tableting conditions are 28 cylindrical punches, main pressure 1400kg / cm ² , preload 140kg /
cm ² , turntable speed 10 rpm, compression stagnation time 0.06
Table 1 shows the temperature of the mixture for tableting and the temperature of the punch and the mortar under the environment of absolute moisture content of 0.005 kg H ₂ O / kg air, with the setting of the second, the filling amount 11.40 g, and the depth of filling the mortar to 10 mm. After changing as described, 1000 tablets were tabletted under each temperature condition, and the adhesion state to the punch was observed. The prepared color developing tablet was a cylindrical type having a diameter of 30 mm and a thickness of about 10 mm.

<< Adhesion to the punch >>: No sticking at all △: One of 28 punches has a small amount of sticking (continuous tableting is possible) ×: There is sticking, continuous tableting is impossible (1000 tablets are punched) Tableted) XX: Adhered immediately after the start of tableting, 1000 tablets could not be tabletted. Further, the obtained tablet-type solid processing agents were evaluated as follows.

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

<< Generation of powder by vibration test >> 40 tablets prepared were manufactured by Konica Co., Ltd .; stored in an eco jet chemical storage cartridge, and a vibration tester BF-UA
A vibration test was performed for 1 hour at 5-67 Hz / 10 min using (manufactured by IDEX), and the powder generation rate was calculated from the weight loss rate before and after the test.

Table 1 shows the above evaluation results.

[0036]

[Table 1]

From the results in Table 1, if the temperature difference between the tableting granules and the punches and dies is 10 ° C or less, tablets having excellent hardness and abrasion resistance can be continuously tableted, preferably 5 ° C. It turns out that

[0038]

According to the present invention, even if at least a part of the powdery raw material for color developing agent containing carbonate as a buffering agent is granulated and compressed into tablets by a continuous tableting machine, No sticking of granules to the punch occurs, and therefore a large amount of color developing tablets having excellent hardness and abrasion resistance can be stably produced.

[Brief description of drawings]

FIG. 1 is a view showing a mechanism of a rotary tableting machine.

[Explanation of symbols]

 1, 2 Pressure roller 3, 4 Punch 5 Turntable 6 Mortar 7 Hopper 8 Powder granules for tableting

Claims (5)

[Claims] 1. A continuous tableting machine, at least a part of which is a granulated product, in which a powdery granule containing a paraphenylenediamine color developing agent and a carbonate is filled in a die and compressed with a pestle. At the time of compression molding in, the difference between the temperature of the powder and granules at the start of compression molding and the temperature of the pestle and die is 10 ° C or less, and the tablet-like solid processing agent for silver halide photographic light-sensitive materials Manufacturing method. 2. The method for producing a solid tablet processing agent for silver halide photographic light-sensitive materials according to claim 1, wherein the tablet solid processing agent has a carbonate content of 25% by weight or more. 3. The environmental condition at the time of compression molding is an absolute water content of 0.
The method for producing a tablet-like solid processing agent for silver halide photographic light-sensitive materials according to claim 1 or 2, wherein the amount is not more than kg H ₂ O / kg air. 4. The method for producing a tablet-like solid processing agent for a silver halide photographic light-sensitive material according to claim 1, wherein compression molding is performed with a compression stagnation time of 0.004 seconds or more. 5. The tablet-shaped solid processing for silver halide photographic light-sensitive material according to claim 1, 2, 3 or 4, wherein compression molding is carried out with a filling depth of the powdery or granular material in the die of 5 mm or more. Method of manufacturing agent.