JP2564825B2 - Method for producing solid chlorine tablet - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a solid chlorine tablet having excellent tableting properties and a high dissolution rate.

As the solid chlorine agent, highly bleached particles, chlorinated isocyanuric acid and the like are used in various fields for sterilization, washing or bleaching. For example, it is used as a sterilizing / disinfecting agent for drinking water, sewage or pool water, and as a sterilizing / cleaning agent for tableware, cooking facilities, and cookware. Further, it is also used for sterilization and bleaching of fibers.

(Prior Art) The commercial form of the solid chlorine agent is powder, granules, and tablets, or powders formed into granules or tablets rather than powders are used because of handling problems. In particular, as a disinfectant for pool water, a method of directly spraying granules and tablets of solid chlorine agent and introducing pool water into a closed system disinfecting device containing solid chlorine agent to dissolve and dissolve the solid chlorine agent The disinfection method by the circulation method of returning the liquid to the pool is adopted.

Although the method of directly spraying granules or tablets directly into pool water is a commonly used method, various measures have been taken so as not to adversely affect swimmers during or after spraying. For example, granules are sized in order to suppress powder standing as much as possible and prevent scattering of powder during spraying. Also, in tablets,
It is designed to prevent swimmers from stepping on the foot or playing with it by collapsing and dispersing at the bottom of the pool in a short time after spraying. As an example of this, in JP-A-51-139628 and JP-A-54-160730, a disintegrating agent is compounded into a tablet containing trichloroisocyanuric acid as a main ingredient, which has low solubility, and immediately disintegrates and disperses in water. Is suggested to do.

Further, even if it is highly soluble such as advanced bleaching powder or alkali metal salt of dichloroisocyanuric acid, in the case of tablets, it is about 1 to 2 for dissolving at a place where water does not move much like the bottom of the pool.
It takes time.

As a method for more rapidly dissolving tablets of an alkali metal salt of dichloroisocyanuric acid, JP-A-56-142210 discloses that an alkali metal salt of dichloroisocyanuric acid is mixed with an alkali metal salt of carbonate or bicarbonate and a solid organic acid. A method has been proposed in which carbon dioxide gas is generated in water by blending and is dissolved more rapidly by its foaming power. However, the tablet in which the carbonate or bicarbonate is mixed with the solid organic acid is particularly susceptible to moisture, and since moisture in the formulation and moisture is taken from the outside air and reacts, carbon dioxide gas is generated. However, it is necessary to specify the raw materials, manufacturing conditions and packaging materials to eliminate the influence of water, and it is not practical for pools and commercial use.

Granular sodium dichloroisocyanurate tablets with a water content of 7 to 11% by weight are extruded and granulated into a wet cake in the form of somen, and the extruded and granulated product is fluidized and dried to a water content of 7 to 11% by weight. Then, a method has been proposed in which the dried product is molded into a plate shape by using two rolls, crushed and sieved to obtain granules, and the granules are tableted to give tablets (JP-A-55-6201).
1, JP-A-57-203009). This wet granulation method has a problem that an extrusion granulated product is easily pulverized during fluidized drying.

Furthermore, solid chlorine agents are difficult to tablet continuously without a release agent, especially anhydrous sodium dichloroisocyanurate and potassium dichloroisocyanurate, even with a release agent, have a diameter of 20 mm or more and 10 g. It is difficult to continuously press the above-mentioned large tablets.

(Problems to be Solved by the Invention) As described above, the problem of the conventional example is that the dissolution rate of the solid chlorine agent tablet is slow, the problem of pulverization during drying after wet granulation, and the solid chlorine agent is The present inventors have conducted extensive studies in order to solve the problem that continuous tableting was difficult without a release agent. As a result, the wet cake obtained in the production process of the solid chlorine agent is extruded and granulated, and the granulated product in this wet state is formed into a spherical shape using a rolling granulator or a spherical granulator, This is dried and tableted to form a dry powder in the form of a plate with two rolls, and the granules obtained by the dry method of crushing and classifying are compared to tablets to be tablet-dissolved. The present invention has been completed by finding the features that the speed is extremely high and there is no trouble during tableting using a normal single-shot or rotary tableting machine.

An object of the present invention is to provide a method for producing a solid chlorine tablet, which has a high dissolution rate and has no troubles during tableting.

(Means for Solving Problems) The present invention relates to a method for producing a solid chlorine agent tablet from a cake in a wet state obtained in the step of producing a solid chlorine agent, comprising: (a) extruding a cake in a wet state by extrusion granulation; 0.2-5 mm
(B) After granulating the columnar granulated product into a spherical granule having a diameter of 0.2 to 5 mm by a rolling granulator or a spherical granulator, (b) The present invention relates to a method for producing a solid chlorine tablet, which comprises the steps of drying and (d) tableting. Hereinafter, the present invention will be described in more detail.

As the solid chlorine agent used in the present invention, advanced bleaching powder,
They are trichloroisocyanuric acid, anhydrous dichloroisocyanurate or its hydrate, and chlorinated isocyanuric acid such as potassium dichloroisocyanurate and salts thereof.

The raw material used in the present invention is a wet cake obtained by filtering and dewatering from a reaction system in a conventional industrial process for producing a solid chlorine agent. The water content of this wet cake is usually in the range of 10-40% by weight.

In the method of the present invention, spherical granules are granulated by using a rolling mill or a spherical granulator in the above step b), but the above wet cake is directly b-blended by extruding granulation in the step a). )
When the particle size is increased by using a rolling granulator or a spherical granulator in the process, a lump-shaped non-uniform mass is formed, and when the granulated product is further dried, it is pulverized. Further, if the columnar particles after the extrusion granulation in the step a) are directly dried in the step c), they are also pulverized. However, if the rolling granulation method is applied after extrusion granulation of the wet cake, strong spherical granules with almost no pulverization even in the subsequent drying step or granule transfer can be obtained. The obtained granules are spherical with a uniform diameter in appearance and have high free-flowing properties. The diameter of the spherical granules of the solid chlorine agent depends on the diameter of the small holes used in the extrusion granulation. The preferable diameter of the spherical granule is 0.2 to 5 mm, and the more preferable diameter is 0.4 to 2 mm. Therefore, the diameter of the small holes of the extrusion granulator used is 0.2-5 m
m, preferably 0.4-2 mm. The extruded granules having a diameter of 0.2 to 5 mm, preferably 0.4 to 2 mm, are molded into a spherical shape by a rolling granulator or a spherical sizing machine to obtain a spherical granule of a desired shape. can get.

The extrusion granulator to be used includes a screw type extrusion granulator, a roll type extrusion granulator, a blade type granulation machine and the like, but a screw type extrusion granulator is preferable.

As a granulator for granulating into a spherical shape, a rolling granulator or
A spherical particle sizer can be used. The rolling granulator is preferably a drum type or a dish type granulator. The spherical granulator is generally called a marmelizer. This is to make wet granules spherical by centrifugal force and frictional force due to unevenness on the plate on a horizontally rotating grooved plate, which makes the inner wall of the casing into a donut shape and twists like rope rope. While rotating, it has a mechanism that makes it spherical.

Although the granules granulated in the spherical shape in the step b) are dried in the step c) in this way, there are various drying methods, and the fluidized drying method is preferable.

The temperature at the time of this drying must be 45 to 55 ° C, which is a temperature within which desorption of water of crystallization does not occur when dihydrate of sodium dichloroisocyanurate is obtained, but other solid chlorine is used. The agent may be higher than this temperature. The preferable temperature at this time is 70 to 130 ° C. It is desirable that the content of free water in the solid chlorine agent is 2% or less by this drying.

The bulk density of the spherical granules of the solid chlorine agent thus obtained is somewhat different depending on the solid chlorine agent, but is 0.5 to 0.9 g / cm ³ for the chlorinated isocyanuric acid compound, and 0.7 to 1.0 g for the advanced bleaching powder. / cm ³ , which is lower than the bulk density of the granules obtained by dry granulation.

The surface of the granules obtained by the method of the present invention is high, but the inside is porous, so that the bulk density is lower than that of the dry granulated product and there is no pulverization. Further, since it has a spherical shape, the fluidity is remarkably good.

Next, the spherical granules obtained by the above-mentioned methods a) to c) are used to make tablets in the step d). As a tableting method, a single shot tableting machine, a rotary tableting machine or the like which is commonly used is used for tableting. When the spherical granules obtained by the method of the present invention are used, the fluidity is good, so that the raw material can be fed smoothly and quantitatively, and even when continuously compressed, problems such as a capping phenomenon occur. Therefore, continuous tableting can be performed with the surface, density, hardness and the like of the obtained tablet being always stable. In particular, conventionally, solid chlorine agents such as anhydrous sodium dichloroisocyanurate and potassium dichloroisocyanurate have been difficult to be continuously tableted even if an auxiliary agent such as a release agent is used, but the method of the present invention is easy. It became possible to continuously tablet.

Further, the tablet of the present invention is characterized by having an extremely high dissolution rate as compared with the case of the tablet using the granules obtained by the conventional dry method.

At the time of tableting, stearates, orthoboric acid, talc and the like which are commonly used as a release agent may be added to the spherical granules. If necessary, an inorganic builder,
You may mix | blend surfactant, a foaming agent, etc.

In addition, when making spherical granules, binders that are usually used to increase the hardness of granules are added, and lubricants such as stearate, orthoboric acid, and talc are added to reduce friction in extrusion molding. You may.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the technical scope of the present invention is not limited thereto.

Example 1 (Sodium dichloroisocyanurate) (Production of granules) A sodium dichloroisocyanurate in a wet state having a water content of 21.6% by weight was extruded and granulated by a pelletizer (Peretable EXD-60 manufactured by Fuji Paudal Co., Ltd.). This apparatus was also used in Comparative Examples), and about 20 kg of wet columnar particles having a diameter of 1 mm and a length of 2 to 5 mm were obtained at a granulation rate of 50 to 60 kg / hour. The columnar particles were charged at a rate of 0.5 kg at one time by using a rolling granulator (Marumerizer Q-230 manufactured by Fuji Paudal Co., Ltd., which was also used in the following Examples and Comparative Examples). , The diameter is 1.0-1.8mm in about 2 minutes
Wet spherical granules were obtained. Then, the wet spherical granules were 0.8 kg at a time in a fluid dryer (Midget dryer MD-A-200 manufactured by Fuji Paudal Co., Ltd., which was also used in the following Examples and Comparative Examples). 5 to 1
It was charged in 5 minutes, and air was blown at a hot air temperature of the inlet of 85 to 95 ° C. to dry it. It should be noted that the drying was finished at the point where the temperature of the exhaust gas started to rise rapidly. When the water content of the spherical granules was high, the temperature of the exhaust gas at the outlet was 30-40 ℃. There was almost no pulverization during this drying. Water content 0.7
%, The bulk density was 0.69 g / cm ³ , and the spherical granules of sodium dichloroisocyanurate having a diameter of 1 to 1.8 mm were obtained.

(Production of Tablets and Evaluation of Tabletability) 0.2 g by weight of sodium stearate as a release agent was mixed with the spherical granules thus obtained 1
Rotary tablet machine weighs 0 kg with a diameter of 30 mm and a thickness of 11 to 15 m
Tablets measuring 20 m and weighing 20 g were continuously molded. At this time, as an evaluation of the tableting property, the squeaking noise when the tablet is discharged from the mold (mill) during tableting and the appearance of the obtained tablet are observed for the edge collapse or the side and surface scratches of the tablet. did. As a result, a normal tablet was obtained in which there was no creaking noise, there was no disintegration at the edge of the tablet, or there were no scratches on the side or surface of the tablet, and the tablet density, hardness, etc. were almost constant from the start to the end of continuous tableting. .

Comparative Example 1 Wet cylindrical particles having a diameter of 1 mm and a length of 2 to 5 mm obtained by the extrusion granulator used in Example 1 were not granulated using a rolling granulator. Direct air flow drying at an inlet temperature of 85-95 ℃, but almost all of it was pulverized.

Comparative Example 2 The raw material used in Example 1 was directly granulated by a mobile granulator without extrusion granulation. Only 2-50 mm lump-shaped and non-uniform granules adhered to the wall surface and the bottom surface of the tumbling granulator were obtained, and the granules were dried at an inlet temperature of 85-95 ° C, but almost all were pulverized. Comparative Example 3 (Tabletting of sodium dichloroisocyanurate granules obtained by a dry method) A powder of sodium dichloroisocyanurate sodium having a water content of 0.6% by weight (150 mesh pass product) was rotated by a roller compactor at a rotation speed of 15 times / min and a hydraulic pressure. 75kg / cm ³ , compression pressure (linear pressure) 1.5 ton / cm, granulation speed 90kg / h, width 60mm,
A plate-shaped molded product having a thickness of 1.5 mm was obtained, which was further crushed and sieved to obtain granules of 990 to 1400 µ. 10 kg of the granules mixed with 0.2% by weight of sodium stearate as a release agent was tabletted in the same manner as in Example 1. There is a loud creaking noise when the tablet is discharged from the mold (mill) during tableting,
Observing the appearance of the obtained tablets, it was found that the edges had many collapsed portions and there were many vertical scratches on the side surfaces, and when continuously tableted, the edge collapsed portions and the amount of scratches were gradually increased. As a result, the number of tablets has increased, making continuous tableting difficult.

Example 2 (sodium dichloroisocyanurate) The same spherical granules as in Example 1 were used, and tableting was performed in the same manner as in Example 1 except that 5% of orthoboric acid was blended as a release agent. There was no creaking noise when the tablet was ejected from the mold (mill) during tableting, and the appearance of the obtained tablet was normal, and there were no broken edges or side and surface scratches. .

Comparative Example 4 (Tabletting of granules of sodium dichloroisocyanurate obtained by the dry method) 5% of the same orthoboric acid as in Example 2 as a release agent was added to the granules of sodium dichloroisocyanurate obtained by the method of Comparative Example 3. Then, the tablets were compressed in the same manner as in Example 1. There is a loud creaking noise when the tablet is discharged from the mold (mill) during tableting,
When the appearance of the obtained tablet was observed, there was a part where the edge was broken and there were many vertical scratches on the side surface, and similar to Comparative Example 3, continuous tableting was difficult.

Example 3 (sodium dichloroisocyanurate) The same spherical granules as in Example 1 were used and tableting was carried out in the same manner as in Example 1 without compounding the release agent. There was some creaking noise when the tablet was ejected from the mold (mill) during tableting, but it was not a problem, and when observing the appearance of the obtained tablet, there were some parts with broken edges, There were no scratches on the side or surface, and it was not a problem.

Comparative Example 5 (Tabletting of granules of sodium dichloroisocyanurate obtained by the dry method) The granules of sodium dichloroisocyanurate obtained by the method of Comparative Example 3 were carried out in the same manner as in Example 3 without adding a release agent. Tableted in the same manner as in Example 1. When the tablet was discharged from the mold (die) during tableting, the squeaking noise was loud, and when observing the appearance of the tablet obtained, there were some parts with broken edges and many vertical scratches on the side. As with No. 3, continuous tableting was difficult.

Example 4 (sodium dichloroisocyanurate dihydrate) The same raw materials as in Example were used and the same procedure was performed. However, the inlet gas temperature during fluidized drying was set to 45 to 55 ° C. There was almost no pulverization during fluidized drying. Bulk density 0.78 g / cm ³ , diameter 1.0 to 1.7 mm
Spherical granules of sodium dichloroisocyanurate dihydrate were obtained. Water content is 13.9% by weight including crystal water
Met. 10 kg of the spherical granules thus obtained were tabletted in the same manner as in Example 1 without adding a release agent. There was no creaking noise when the tablet was ejected from the die (mill) during tableting, and when observing the appearance of the obtained tablet, a normal tablet was obtained without broken edges or side and surface scratches. It was

Comparative Example 6 The columnar particles obtained in Example 2 were directly subjected to fluidized drying at an inlet temperature of 45 to 55 ° C. without granulation using a rolling granulator, and dichloroisocyanuric acid dihydrate was used. I tried to obtain granules of the product, but almost all of them were pulverized.

Comparative Example 7 (Tabletting of granules of sodium dichloroisocyanurate dihydrate obtained by the dry method) A powder of sodium dichloroisocyanurate dihydrate having a water content of 13.6% by weight (150 mesh pass product) was used as Comparative Example 3. The same procedure was followed to obtain granules of 990 to 1400μ. This granule 10k
Tablets were compressed in the same manner as in Example 1. The squeaking noise when the tablet was ejected from the mold (mill) during tableting was slightly loud, and when the appearance of the obtained tablet was observed, there was some edge breakage and some vertical scratches on the side surface. In addition, when tablets are continuously pressed, the portion where the edge is broken and the amount of scratches are gradually increased.

Example 5 (trichloroisocyanuric acid) Example 5 (trichloroisocyanuric acid) was carried out in the same manner as in Example 1 except that trichloroisocyanuric acid in a wet state having a water content of 15.2% by weight was used. There was almost no pulverization during fluidized drying. Spherical granules of trichloroisocyanuric acid having a bulk density of 0.85 g / cm ³ , a water content of 0.3% by weight and a diameter of 1 to 1.7 mm were obtained. 10 kg of the spherical granules thus obtained were tabletted in the same manner as in Example 1 without adding a release agent. There was little squeaking noise when the tablet was ejected from the die (mill) during tableting, and the appearance of the obtained tablet was observed.

Example 6 (potassium dichloroisocyanurate) Example 6 was carried out in the same manner as in Example 1 except that potassium dichloroisocyanurate having a water content of 20.7% by weight was used. There was almost no pulverization during fluidized drying. Bulk density 0.79g / cm
^3. Spherical granules of potassium dichloroisocyanurate having a water content of 0.4% by weight and a diameter of 1 to 1.7 mm were obtained. 10 kg of the spherical granules thus obtained were tabletted in the same manner as in Example 1 without adding a release agent. There was a slight creaking noise when the tablet was discharged from the mold (mill) during tableting, but the appearance of the obtained tablet was observed, and it was found that the edges did not collapse and the side surface scratches were considerably reduced.

Example 7 (potassium dichloroisocyanurate) The spherical granules of potassium dichloroisocyanurate obtained by the method of Example 6 were mixed with 0.2% by weight of sodium stearate as a releasing agent, and 10 kg of the mixture was prepared in the same manner as in Example 1. Tableted.

There was no creaking noise when the tablet was discharged from the die (mill) during tableting, and the appearance of the obtained tablet was observed, and the edges were not distorted, and normal tablets were obtained with no side or surface scratches. .

Example 8 (advanced bleaching powder) The same operation as in Example 1 was carried out except that a highly bleached powder in a wet state having a water content of 22.4% was used. There was almost no pulverization during fluidized drying. Bulk density 0.85 g / cm ³ , water content 1.7% by weight,
Spherical granules of highly bleached powder having a diameter of 1 to 1.7 mm were obtained. 10 kg of the spherical granules thus obtained were tabletted in the same manner as in Example 1 without adding a release agent. There was no creaking noise when the tablet was discharged from the die (mill) during tableting, and the appearance of the obtained tablet was observed, and the edges were not distorted, and normal tablets were obtained with no side or surface scratches. .

Comparative Examples 8 to 10 The columnar particles obtained in Examples 5, 6, and 8 were directly subjected to fluidized drying at an inlet temperature of 85 to 95 ° C without granulation using a rolling granulator. Almost all of it has been pulverized.

Comparative Examples 11 to 13 The wet cakes used in Examples 5, 6 and 8 were put into a direct rolling type granulator without being extruded and granulated. In the same manner as in Comparative Example 2, only granular and non-uniform granules of 2 to 50 mm attached to the wall surface and the bottom surface of the rolling granulator were obtained, and the inlet temperature was 85 to 95.
Although it was dried at ℃, almost all powdered.

Comparative Examples 14 to 16 (tablet compression of granules obtained by dry method) The following solid chlorine powder (150 mesh pass product) was dry granulated in the same manner as in Comparative Example 3 to prepare granules of 990 to 1400μ, Tableted in the same manner as in Example 1.

Comparative Example 14; Trichloroisocyanuric acid Comparative Example 15; Potassium dichloroisocyanurate Comparative Example 16; Advanced bleaching powder Both squeaky sounds when the tablet was discharged from the mold (mill) during tableting In each case, the edges were broken, and the side surface had many scratches, which made continuous tableting difficult as in Comparative Example 3.

[Evaluation of dissolution rate of tablets]

Water of 17 ± 1 ℃ is continuously passed through a water tank of 400 × 400 × 100mm in length, width and depth at a rate of 3 per minute, the liquid level is kept constant by overflow and the depth is 50mm below the liquid level. A 4-mesh stainless steel wire net was provided on the plate, and the tablets of the solid chlorine agent obtained in Examples and Comparative Examples were placed on the table to measure the dissolution rate of the tablets. In the solid chlorine agent, sodium dichloroisocyanurate and its dihydrate swell and disintegrate in water in a short time, so that the dispersed sodium dichloroisocyanurate and its dihydrate are completely (100%) dissolved. The time was measured.

On the other hand, in the case of tablets of trichloroisocyanuric acid, potassium dichloroisocyanurate, and advanced bleaching powder, the moisture on the tablet surface is wiped off at regular intervals, the weight is measured after that, and the weight of each time is plotted in a graph, and the result The time required for the tablets to dissolve by 50% was measured. The results are shown in Table 1.

Continuation of front page (56) Reference JP-A-57-28071 (JP, A) JP-A-60-231664 (JP, A) JP-A-55-57576 (JP, A) JP-A-57-31862 (JP , A) JP-A-60-129130 (JP, A) JP-A-61-245833 (JP, A)

Claims (7)

(57) [Claims] 1. A method for producing a solid chlorine agent tablet from a cake in a wet state obtained in the step of producing a solid chlorine agent, comprising: (a) 0.2-5 mm in diameter of a cake in a wet state by extrusion granulation.
(B) After granulating the columnar granulated product into a spherical granule having a diameter of 0.2 to 5 mm by a rolling granulator or a spherical granulator, (b) A method for producing a solid chlorine tablet, comprising the steps of drying and (d) tableting. 2. The method for producing a solid chlorine agent tablet according to claim 1, wherein the solid chlorine agent is a chlorinated isocyanuric acid compound. 3. The chlorinated isocyanuric acid compound is at least one compound selected from trichloroisocyanuric acid, anhydrous dichloroisocyanurate or a hydrate thereof, and potassium dichloroisocyanurate. A method for producing a solid chlorine tablet according to item 2. 4. The method for producing a solid chlorinated tablet according to claim 2, wherein the spherical granules of the chlorinated isocyanuric acid compound have a bulk density of 0.5 to 0.9 g / cm ³ . 5. The method for producing a solid chlorine agent tablet according to claim 1, wherein the solid chlorine agent is a highly bleached powder. 6. The bulk density of the spherical granules of advanced bleached powder is 0.7 to 1.0.
The method for producing a solid chlorine tablet according to claim 5, wherein the method is g / cm ³ . 7. The method for producing a solid chlorine tablet according to claim 1, wherein the wet cake has a water content of 10 to 40% by weight.