JPS5951948B2 - Rapidly disintegrating chlorinated isocyanuric acid molded product in water - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel chlorinated isocyanuric acid moldings that exhibit rapid and fine disintegration in water.

Conventionally, chlorinated isocyanuric acid has been frequently used as a disinfectant, a cleaning agent, a bleaching agent, etc., because it exhibits the property of trihydrolyzing in water and releasing chlorine.
Powdered products tend to crumble during use or handling;
In addition, it is generally not preferred because measuring operations are troublesome, and granules or tablets are desired.
However, because chlorinated isocyanuric acid has a low saturation solubility in water at room temperature of around 1.2%, it is difficult to quickly distribute a sufficient amount of available chlorine throughout the water by simply adding tablets to the water. cannot be supplied as such. In order to solve this problem, there has been a known proposal to pre-contain a component in the tablet that causes the tablet to disintegrate when it is placed in water, but there are practical problems and there is still no sufficient solution. is not obtained. For example, carbonated soda,
A method in which a substance that produces an effervescent effect, such as sodium bicarbonate, is mixed into the tablet is not preferred because the disintegration particles do not become fine in water, and deterioration is likely to occur even when stored in a closed container. Another example is a proposal (Japanese Patent Application Laid-open No. 139628/1983) in which an anhydrous salt of sodium dichloroisocyanurate is included in tablets, but this tablet tends to deteriorate during storage, i.e. Chlorinated isocyanuric acid tends to decompose during long-term storage, which not only reduces the effective chlorine content but also damages storage containers and reduces disintegration in water. As a result of various experimental studies on the disintegration properties in water of tablets containing chlorinated isocyanuric acid, the present inventors found that boric anhydride (B
When granules or tablets containing calcium salts of 2O3) and carboxymethyl cellulose are placed in water, they rapidly and minutely disintegrate, and chlorine is quickly supplied throughout the water, and the granules or tablets mentioned above discovered that the above-mentioned deterioration does not occur during storage in a normal closed container, and that it can be stored extremely stably for a long period of time, and completed the present invention.

An object of the present invention is to provide a press-molded product containing chlorinated isocyanuric acid that quickly disintegrates into fine particles when placed in water, and another object of the present invention is to provide a press-molded product containing chlorinated isocyanuric acid that quickly disintegrates into fine particles when placed in water. The object of the present invention is to provide a press-molded product containing chlorinated isocyanuric acid that can be stored stably over a period of time without deterioration.

The water-disintegrating chlorinated isocyanuric acid molded article of the present invention is made of 100 parts by weight of a composition containing powdered or granular chlorinated isocyanuric acid as a main component and 0.3 parts by weight of boric anhydride.
It is characterized by being formed by pressure molding a mixture of ~10 parts by weight and 0.05 to 10 parts by weight of calcium salt of carboxymethyl cellulose. The chlorinated isocyanuric acid used in the present invention is trichloroisocyanuric acid, dichloroisocyanuric acid, or a mixture thereof, and usually,
It can be manufactured by hand as a powder or granule industrial product with a water content of 1% or less. The composition containing chlorinated isocyanuric acid as a main component used in the present invention includes the above-mentioned powder or granular chlorinated isocyanuric acid, and other auxiliary agents, fillers, and other auxiliary ingredients. Examples of the above-mentioned auxiliary agents and fillers include anhydrous sodium carbonate and sodium bicarbonate as blowing agents, orthoboric acid as a molding lubricant, and sodium stearate as a filler. Examples include common salt, mirabilite, etc. The composition containing the above-mentioned chlorinated isocyanuric acid as a main component must be in the form of powder or granules. Alternatively, disintegration occurs down to the size of granular particles. Therefore, the particle size of the powder or granules of the above composition is preferably as small as possible, but a particle size of about 20 to 1400 microns is usually sufficient.

Boric anhydride used in the present invention is represented by the chemical formula B2O3, and is usually an industrial product in the form of a fine powder of about 70 to 300 microns. This boric anhydride has the effect of strongly disintegrating the molded product of the present invention when it is placed in water and comes into contact with water. When storing the molded product of the present invention, it acts to prevent deterioration of the molded product and maintain the molded product stably for a long period of time. On the other hand, molded products containing chlorinated isocyanuric acid that do not contain boric anhydride do not contain chlorinated The decomposition of isocyanuric acid progresses gradually, and the accumulated decomposed gas can cause damage to the container, cause corrosion, and workers may suffer damage when opening the container. The chlorinated isocyanuric acid-proprietary molded product of the present invention does not cause such problems at all. The calcium salt of carboxymethyl cellulose used in the present invention usually has a degree of polymerization of about 50 to 1000 and a degree of substitution of 0.2 or more.

), which is water-insoluble and has a white particle size of 20
A powder of about 200 μm is preferable. This Ca-CMC also prevents deterioration of the molded product and provides long-term stability to the chlorinated isocyanuric acid-proprietary molded product of the present invention when stored in a closed container. When it comes into contact with it, it acts to quickly disintegrate the molded product. The chlorinated isocyanuric acid-containing molded article of the present invention comprises the chlorinated isocyanuric acid-containing composition, the boric anhydride in an amount of 0.3 to 10%, and 0.05 to 10% of the composition.
% of the above Ca-CMC. Mixing is easily carried out using a conventional mixer, and the more uniform the better, resulting in uniform disintegration when the molded product is placed in water. Of course, in the above mixing, other arbitrary components may be mixed as long as the purpose of the present invention is achieved. For example, if a small amount of sodium stearate is added as a molding lubricant, a mixture with good moldability can be obtained. In the above mixing, the mixing ratio of boric anhydride is 0.
If it is less than 3, when the obtained molded product is placed in water, rapid and fine particle disintegration is difficult to occur throughout the molded product, and it does not have a sufficient stabilizing effect when stored in a closed container. . The higher the mixing ratio of boric anhydride, the more effective it becomes, but when it is mixed at a ratio as high as 10% or more, there is no difference in the above effects.
The content of chlorinated isocyanuric acid in the molded product decreases,
Practically unfavorable. Regarding Ca-CMC, for the same reason as above, the mixing ratio is 0.05~
10% is preferred. A surprising effect of the present invention is that both the boric anhydride and Ca-CMC components act mutually to cause the molded product to disintegrate in water in an extremely short time. For example, a tablet obtained by mixing only 4 parts by weight of boric anhydride with 100 parts by weight of the chlorinated isocyanuric acid-containing composition takes 5 minutes and 11 seconds to completely disintegrate in water; Ca-CMC only 4
The tablet obtained by mixing 2 parts by weight of boric anhydride and 2 parts by weight of Ca{MC takes 2 minutes and 17 seconds to completely disintegrate in water, whereas the tablet obtained by mixing 2 parts by weight of boric anhydride with 2 parts by weight of Ca{MC tablet takes only 5 minutes to completely disintegrate in water.
It only takes 9 seconds. In order to produce such a mutually beneficial effect, the mixing ratio of boric anhydride and Ca-CMC should be 1 part by weight of boric anhydride to 1 part by weight of Ca-CMCO. It is preferably 1 to 5.0 parts by weight, particularly 0.3 to 3.0 parts by weight. As the mixing ratio of boric anhydride and Ca-CMC in the molded product decreases, the time required for the entire molded product to disintegrate in water becomes longer, and the total mixing ratio of both boric anhydride and Ca-CMC decreases to chlorinated isocyanuric acid. However, if the concentration is less than 0.3%, the obtained molded product will gradually disintegrate from the surface in water, and the disintegrated particles will peel off into the water. For example, when the tablets are to be supplied little by little into flowing sewage, the method of immersing tablets with such a low mixing ratio in sewage water can
Since that purpose is achieved, moldings with such low mixing ratios can also be used. However, except for the special uses mentioned above, it is generally desired that the entire molded product disintegrates quickly. The chlorinated isocyanuric acid-containing molded article of the present invention is obtained by pressure molding the mixture obtained by the above mixing.

The shape of the molded product may be arbitrary depending on the purpose of use, and may be one that can be molded by a normal pressure molding method. for example,
Diameter 1 to 5 (: 7RL, height 0.
Tablets with a size of about 5 to 5 cm, plate-shaped products with a thickness of about 1 to 3 ml obtained by using a contact machine, or flake-shaped products obtained by crushing the same can be mentioned. In the case of tableting, pressure molding is preferably about 100 to 800 kg/(-JmoVF. If the tableting pressure is less than 50 kg/Cil, the shape of the molded tablet is likely to collapse during handling or storage/transportation. , a pressure of 900 kg/Cil or more is unnecessary and causes unnecessary energy loss. When using a contact machine, a pressure of about 300 to 3000 kg/Cil is preferable for the same reason as above. The chlorinated isocyanuric acid-containing molded article of the present invention is usually once sealed in a plastic container, bag, etc., and if necessary, further stored in a cardboard box, metal container, etc., for a long period of time. For a long period of time, no deterioration occurs, and when the package is opened and put into water, the whole disintegrates quickly, usually within 2 minutes, and the finely disintegrated chlorinated isocyanuric acid particles are absorbed by the shaking of the water. In some cases, further dispersion occurs and a rapid supply of chlorine throughout the water is achieved by dissolution and hydrolysis.

The chlorinated isocyanuric acid-containing molded article of the present invention is useful for purifying sewage, sterilizing swimming pools, sterilizing water for washing dishes, etc. The present invention will be described in more detail below with reference to Reference Examples, Examples, and Comparative Examples, but the technical scope of the present invention is not limited thereby.

First, the test method for disintegration in water and the test method for storage stability will be explained.

Test method A (Tablet disintegration test in water) In a container made of a polyvinyl chloride cylinder with an inner diameter of 40 □l and a height of 55 mm, stainless steel wire meshes with 8 meshes were attached to the top and bottom as the bottom mesh and lid mesh. A sample tablet weighing 30 g was suspended in a large beaker containing water at 25°C via a holder, and immediately shaken at a rate of 30 times/min with an underwater shaking width of 50 m. The disintegrated particles are caused to fall out of the container through the screen by vertical movement, and the time required for the entire amount to fall out of the screen is measured.

Test method B (disintegratability test of granules in water) ~Instead of the tablet container in test method A above, an inner diameter of 12
(V7z, a container made of polyvinyl chloride with a height of 15 mm and stainless steel wire mesh with 40 meshes attached to the top and bottom as the bottom mesh and lid mesh, was used, and 19 amounts of test granules were placed in it, The time required for the entire amount to fall out of the net is measured in the same manner as in Test Method A above.

Test method C (Storage stability test for molded products) 3 for granules in a three-necked glass container with an internal volume of 500 g
01. For tablets, put one tablet (301) trial sample, seal No. 10 with a rubber stopper, attach glass stoppers with valves to No. 20 and No. 30, close the valves, and store in a constant temperature room at 35 ° C for 10 days. Store it still.

After that, a dry nitrogen gas conduit is connected to the 20th pipe, and the 30th pipe is connected to the dry nitrogen gas conduit.
A conduit for passing 50 g of 0.5 caustic soda aqueous solution is connected to the valve, and immediately after the above storage period, both valves are opened, and the second valve is opened.
Dry nitrogen was introduced from No. 0, and exhaust gas from No. 30 was introduced into a caustic soda aqueous solution to absorb decomposition gas. After aeration, add 0.22% potassium iodide to the caustic soda aqueous solution.
was added and titrated with a 1/100 normal sodium thiosulfate aqueous solution under acetic acid acidic conditions using starch as an indicator to determine the amount of available chlorine absorbed in the caustic soda aqueous solution. This effective chlorine amount was taken as the total amount of chlorine gas and chlorine nitrogen gas generated from trichloroisocyanuric acid. Reference Example 1 Trichloroisocyanuric acid powder with a moisture content of 0.3% and a particle size of 50 to 100 μm was processed using a hydraulic roll drying granulator.
The mixture was molded into a plate shape with a thickness of 2 mm under a compression pressure of 1500 kg/cm, then crushed, and further sieved through 10 mesh and 32 mesh to obtain flaky granules with a particle size of 10 to 32 mesh.

The obtained granules were then tested for disintegration in water and storage stability according to Test Methods B and C, and the results shown in Table 1 were obtained. Reference Example 2 Molded into granules in the same manner as Reference Example 1, except that dichloroisocyanuric acid with a water content of 0.7% and a particle size of 50 to 100 μm was used instead of trichloroisocyanuric acid in Reference Example 1. Furthermore, the disintegration properties in water and storage stability were tested, and the results shown in Table 1 were obtained.

Reference Example 3 A mixture of the granules obtained in Reference Example 1 and sodium stearate, a molding lubricant, with a water content of 0.6% and a particle size of 20 to 70μ in an amount of 0.2% was subjected to rotary continuous tableting. The tablets were compressed using a machine at a tableting pressure of 300 kg/Crl to obtain one disc-shaped trichloroisocyanuric acid tablet having a weight of 301 cm, a diameter of 351 Em, and a height of 17 cm.

When this tablet was tested for disintegration in water and storage stability according to Test Methods A and C, the results shown in Table 1 were obtained. Reference Example 4 Dichloroisocyanuric acid tablets were obtained in the same manner as Reference Example 3, except that the granules obtained in Reference Example 2 were used instead of the granules obtained in Reference Example 1, and the disintegration in water and storage were further evaluated. The stability was tested and the results shown in Table 1 were obtained.

As shown in the table, the granules and tablets of Reference Examples 1 to 4 all had poor storage stability, releasing a considerable amount of decomposed chlorine even in closed containers, and did not disintegrate in water. Dissolution of chlorinated isocyanuric acid only occurs from the surface of the molded product.

Examples 1 to 7 The same trichloroisocyanuric acid powder used in Reference Example 1, boric anhydride powder with a particle size of 70 to 120μ, and self-hydration rate 4
．． 5% Ca-CMC powder with a particle size of 30 to 60μ
After mixing in the ratios listed in the table, they were formed into granules in the same manner as in Reference Example 1, and further tested for disintegration in water and storage stability, and the results listed in Table 2 were obtained.

Examples 8 to 10 Granules were formed in the same manner as in Example 1, except that the same dichloroisocyanuric acid used in Reference Example 2 was used instead of trichloroisocyanuric acid in Example 1. When the storage stability was tested, the results shown in Table 2 were obtained.

Examples 11-15 The same trichloroisocyanuric acid powder or dichloroisocyanuric acid powder as used in the above examples, boric anhydride, Ca-CMC, water content 0.6%, particle size 20-70μ
After mixing sodium stearate in the proportions listed in Table 3, tablets were obtained by the same tableting method as in Reference Example 3, and further tested for disintegration in water and storage stability. Got the results.

Examples 16 to 20 Sodium stearate having a water content of 0.6% and a particle size of 20 to 70μ was mixed into the granules obtained in Examples 1 to 9 above in an amount of 0.2%, and the mixture was prepared as described in Reference Example 3. The tablets were formed into tablets according to the tableting method described in Table 4, and further tested for disintegration in water and storage stability, and the results shown in Table 4 were obtained.

Examples 21 and 22 The same boric anhydride and Ca as used in the above example were added to the trichloroisocyanuric acid granules obtained in Reference Example 1.
- After mixing CMC and sodium stearate in the ratio shown in Table 5, a trichloroisocyanuric acid tablet was obtained in the same manner as in Reference Example 3, and further tested for disintegration in water and storage stability. The results were obtained.

Examples 23 and 24 Dichloroisocyanuric acid tablets were obtained in the same manner as in Example 21, except that the dichloroisocyanuric acid granules obtained in Reference Example 2 were used instead of the trichloroisocyanuric acid granules in Example 20. Furthermore, when the disintegration property in water and the storage stability were tested, the results shown in Table 5 were obtained.

Comparative Examples 1 to 7 To the same trichloroisocyanuric acid powder as that used in Reference Example 1, anhydrous salt of sodium dichloroisocyanurate having a water content of 0.7% and a particle size of 50 to 100 μ, and the same as that used in the example were added. After mixing the same boric anhydride or Ca-CMC at the ratio listed in Table 6, it was formed into granules in the same manner as in Reference Example 1, and further tested for disintegration in water and storage stability.
The results listed in Table 6 were obtained.

For the molded product of the above example obtained by mixing boric anhydride and Ca-CMC, the same level of boric anhydride or Ca-CMC was mixed.
Comparative molded products with a mixing ratio of are all poor in disintegration in water. Comparative Examples 8 and 9 Molded into granules in the same manner as Comparative Examples 3 and 6 except that the same dichloroisocyanuric acid powder as that used in Reference Example 2 was used instead of trichloroisocyanuric acid in Comparative Example 1, When tested for disintegration in water and storage stability,
The results listed in Table 6 were obtained.

Comparative Examples 10 and 11 The same trichloroisocyanuric acid powder as used in Reference Example 1 was added with the same boric anhydride or Ca-C as described above.
After mixing 4% MC and 0.2% sodium stearate, it was formed into a saturated tablet using the tableting method in Reference Example 3 and tested for disintegration in water and storage stability, and the results shown in Table 7 were obtained. Obtained.

Comparative Examples 12 to 15 To the granules obtained in Reference Examples 1 and 2, 0.2% of the same sodium stearate as above and the same boric anhydride or Ca-CMC as above were added in the ratio shown in Table 8. After mixing, the mixture was formed into tablets by the saturation method of Reference Example 3, and further tested for disintegration in water and storage stability, and the results shown in Table 8 were obtained.

Comparative Examples 16 to 20 The granules obtained in Comparative Examples 3, 5, 6, 8 or 9,
After mixing 0.2% of the same sodium stearate as above, it was compressed into tablets in the same manner as in Reference Example 3, and the resulting tablets were tested for disintegration in water and storage stability. However, the results shown in Table 8 were obtained.

Claims (1)

[Claims] 1 100 parts by weight of a composition containing powdered or granular chlorinated isocyanuric acid as a main component and 0.3 to 0.3 to boric anhydride
1. A rapidly disintegrating chlorinated isocyanuric acid molded product, characterized in that it is formed by pressure molding a mixture of 10 parts by weight of calcium salt of carboxymethyl cellulose and 0.05 to 10 parts by weight of calcium salt of carboxymethyl cellulose.