A chlorinated isocyanuric acid composition with excellent storage stability.

Abstract

To provide a chlorinated isocyanuric acid composition with high storage stability.SOLUTION: A chlorinated isocyanuric acid compound comprises magnesium sulfate and alkali carbonate.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a chlorinated isocyanuric acid composition having excellent storage stability and a tablet which is a pressure molded body thereof.

Background Art

[0002] Chlorinated isocyanuric acid compounds are used as a sterilization and disinfection method for pool water, septic tank water, sewage, effluent water, industrial water, cooling water of cooling towers, and the like. For example, as a method for sterilizing and disinfecting pool water, a tablet containing a chlorinated isocyanuric acid compound is directly put into a pool water tank, or pool circulating water is allowed to flow into a chemical solution containing a chlorinated isocyanuric acid compound to dissolve a part of the chemical, etc. By such a method, active chlorine is gradually released into the pool water to maintain a constant residual chlorine concentration in the pool water.

[0003] Trichloroisocyanuric acid has a high reactivity with water. During its storage, it reacts with trace amounts of moisture contained in the air to generate chlorine gas and nitrogen chloride gas, which are decomposition products of trichloroisocyanuric acid, resulting in a decrease in the amount of active chlorine contained in trichloroisocyanuric acid, the generation of a chlorine odor, and the deterioration of packaging materials in contact with trichloroisocyanuric acid. Therefore, an additive that suppresses the generation of decomposition gases of chlorine and nitrogen chloride is desired so that stable storage can be achieved over a long period.

[0004] <​​​​​​​​​​​​​​​​​​​

[0006] Chlorinated isocyanuric acid compositions are often used in tablet form to facilitate the adjustment of dissolution time, control of the chlorine concentration in the added water, and handling. However, since anhydrous magnesium sulfate expands to more than 2 when it absorbs water, tablets of a chlorinated isocyanuric acid composition, which combines magnesium sulfate with a chlorinated isocyanuric acid compound, had a problem in that the magnesium sulfate would expand when it absorbed moisture from the air during storage, causing the tablets to disintegrate. Furthermore, if the amount of magnesium sulfate was reduced to prevent the tablets from disintegrating, the chlorinated isocyanuric acid compound would decompose during storage, generating chlorine gas that is harmful to the human body.

[0007] In view of the above circumstances, the present invention aims to provide a chlorinated isocyanuric acid composition with excellent storage stability. [Means for solving the problem]

[0008] To achieve the above objectives, the inventors conducted extensive research and, as a result, discovered that by combining a chlorinated isocyanuric acid compound with magnesium sulfate and an alkali carbonate salt, it is possible to suppress the generation of chlorine gas produced by the decomposition of the chlorinated isocyanuric acid compound during storage, even with a reduced amount of magnesium sulfate. This led to the completion of the present invention.

[0009] In other words, the present invention, in its first aspect, provides a chlorinated isocyanuric acid compound with magnesium sulfate This invention relates to a chlorinated isocyanuric acid composition characterized by containing um and alkali carbonate. The second aspect relates to the chlorinated isocyanuric acid composition described in the first aspect, wherein the alkali carbonate salt is substantially sodium carbonate. A third aspect is the chlorinated isocyanuric acid composition according to the first or second aspect, further characterized by the inclusion of a non-halogenated cyclic urea compound. The fourth aspect relates to the chlorinated isocyanuric acid composition described in the third aspect, wherein the non-halogenated cyclic urea compound is substantially cyanuric acid. The fifth aspect relates to a chlorinated isocyanuric acid composition according to the first or second aspect, wherein the chlorinated isocyanuric acid compound is substantially trichloroisocyanuric acid. The sixth aspect relates to a chlorinated isocyanuric acid composition according to the first or second aspect, wherein the amount of magnesium sulfate is 0.01 to 0.4 parts by mass and the amount of alkali carbonate is 0.1 to 1.0 parts by mass per 100 parts by mass of the chlorinated isocyanuric acid compound. The seventh aspect relates to the chlorinated isocyanuric acid composition according to the sixth aspect, wherein the amount of alkali carbonate salt blended is 0.1 to 0.3 parts by mass per 100 parts by mass of the chlorinated isocyanuric acid compound. The eighth aspect relates to the chlorinated isocyanuric acid composition according to the third aspect, wherein the amount of the non-halogenated cyclic urea compound blended is 0.01 to 1.0 parts by mass per 100 parts by mass of the chlorinated isocyanuric acid compound. The ninth aspect relates to the chlorinated isocyanuric acid composition according to the third aspect, wherein the amount of the non-halogenated cyclic urea compound blended is 0.01 to 0.2 parts by mass per 100 parts by mass of the chlorinated isocyanuric acid compound. The tenth aspect relates to a tablet which is a pressure-molded body of a chlorinated isocyanuric acid composition comprising a chlorinated isocyanuric acid compound, magnesium sulfate, and an alkali carbonate salt, wherein, based on the mass of the chlorinated isocyanuric acid compound, the amount of magnesium sulfate is 0.01 to 0.4% by mass, and the amount of alkali carbonate is 0.1 to 0.3% by mass, and based on the total mass of the tablet, the amount of the chlorinated isocyanuric acid compound is 95% by mass or more, and the sum of the amounts of the chlorinated isocyanuric acid compound, the magnesium sulfate, and the alkali carbonate salt is 100% by mass or less. The 11th aspect relates to the tablet according to the 10th aspect, wherein the tablet further contains a non-halogenated cyclic urea compound, the amount of the non-halogenated cyclic urea compound is 0.01 to 0.2% by mass based on the mass of the chlorinated isocyanuric acid compound, and the sum of the amounts of the chlorinated isocyanuric acid compound, magnesium sulfate, alkali carbonate salt, and non-halogenated cyclic urea compound is 100% by mass or less based on the total mass of the tablet. The twelfth aspect relates to the tablet described in the tenth or eleventh aspect, wherein the alkali carbonate salt is substantially sodium carbonate. The 13th aspect relates to the tablet described in the 10th or 11th aspect, wherein the chlorinated isocyanuric acid compound is substantially trichloroisocyanuric acid. The 14th aspect relates to the tablet described in the 11th aspect, wherein the non-halogenated cyclic urea compound is essentially cyanuric acid. [Effects of the Invention]

[0010] According to the present invention, it is possible to provide a chlorinated isocyanuric acid composition that can suppress the generation of chlorine gas due to the decomposition of chlorinated isocyanuric acid compounds during storage. Furthermore, according to the present invention, it is possible to provide a tablet of a chlorinated isocyanuric acid composition that can suppress the generation of chlorine gas due to the decomposition of chlorinated isocyanuric acid compounds during storage and does not disintegrate in shape. [Brief explanation of the drawing]

[0011] [Figure 1] Figure 1 is a schematic diagram illustrating the test method for the tablet disintegration test in the example. [Modes for carrying out the invention]

[0012] The chlorinated isocyanuric acid composition of the present invention is obtained by combining a chlorinated isocyanuric acid compound with magnesium sulfate and an alkali carbonate salt.

[0013] Examples of the chlorinated isocyanuric acid compound used in the present invention include trichloroisocyanuric acid, dichloroisocyanuric acid, and monochloroisocyanuric acid, and preferably trichloroisocyanuric acid. The blending amount of the chlorinated isocyanuric acid compound is not particularly limited, but from the viewpoints of the residual chlorine concentration when dissolved in water and its duration, it is preferably 95% by mass or more in the chlorinated isocyanuric acid composition.

[0014] The magnesium sulfate used in the present invention may be an anhydrous salt or a hydrate, but preferably anhydrous magnesium sulfate. The blending amount of magnesium sulfate contained in the chlorinated isocyanuric acid composition is 0.01 to 0.4 parts by mass, preferably 0.01 to 0.2 parts by mass, based on 100 parts by mass of the chlorinated isocyanuric acid compound. When the blending amount of magnesium sulfate is less than 0.01 part by mass, there is a risk that the chlorinated isocyanuric acid composition reacts with moisture in the atmosphere during storage and decomposition occurs, generating chlorine gas. Also, when the blending amount of magnesium sulfate exceeds 0.4 part by mass, there is a risk of shape collapse due to the volume increase during water absorption and moisture absorption of magnesium sulfate when made into tablets.

[0015] Examples of the alkali carbonate used in the present invention include anhydrous substances and hydrates such as lithium carbonate, sodium carbonate, and potassium carbonate. It can be used alone or in combination of two or more. Among these, substantially sodium carbonate is preferred. Substantially sodium carbonate means that an anhydrous sodium carbonate may contain an alkali hydrogen carbonate or a hydrate that is not substantially added. In the present invention, by blending an alkali carbonate, even when water cannot be completely absorbed by magnesium sulfate, the chlorine gas generated from the chlorinated isocyanuric acid compound can react with the alkali carbonate to produce sodium chloride, so that the generation of chlorine gas can be suppressed. Thereby, the generation of a chlorine odor during storage and preservation can be suppressed.

[0016] The blending amount of the alkali carbonate contained in the chlorinated isocyanuric acid composition is 0.1 part by mass or more, for example, 0.1 to 1.0 parts by mass, preferably 0.1 to 0.5 parts by mass, more preferably 0.1 to 0.3 parts by mass, based on 100 parts by mass of the chlorinated isocyanuric acid compound. When the blending amount of the alkali carbonate is less than 0.1 part by mass, it may not react sufficiently with the chlorine gas generated from the chlorinated isocyanuric acid compound, and a chlorine odor may occur from the chlorinated isocyanuric acid composition during storage and preservation. When the blending amount of the alkali carbonate is increased, the blending ratio of the chlorinated isocyanuric acid compound in the chlorinated isocyanuric acid composition decreases, so there are few advantages in blending more than 1.0 part by mass.

[0017] The chlorinated isocyanuric acid composition of the present invention can contain components such as a non-halogenated cyclic urea compound, a lubricant, an excipient, a dissolution regulator, and a binder as long as the object of the present invention is achieved.

[0018] Chlorinated isocyanuric acid reacts with water to generate hypochlorous acid. When a non-halogenated cyclic urea compound is included, the non-halogenated cyclic urea compound can react with the hypochlorous acid generated from the chlorinated isocyanuric acid to form a chlorinated cyclic urea compound, so the storage stability of the chlorinated isocyanuric acid composition can be enhanced.

[0019] Examples of the non-halogenated cyclic urea compound include ethylene urea, propylene urea, hydantoin, cyanuric acid, and violuric acid, and preferably hydantoin and cyanuric acid. The blending amount of the non-halogenated cyclic urea compound is 0.01 part by mass or more, for example, 0.01 to 1.0 parts by mass, preferably 0.01 to 0.2 parts by mass, based on 100 parts by mass of the chlorinated isocyanuric acid compound.

[0020] When the chlorinated isocyanuric acid composition is compression-molded into tablets, a lubricant can be added from the viewpoints of moldability and脱模性 from the mold. It is possible to prevent chipping and cracking of the tablets during the production and transportation of the tablets. The lubricant is not particularly limited as long as it has the function of improving the fluidity, packing, and adhesion of solid particles, but examples include calcium stearate, magnesium stearate, sodium stearate, sodium benzoate, orthoboric acid, talc, etc., and magnesium stearate is preferred. When a lubricant is added, it can be included in an amount of approximately 0.1 to 1.0% by mass, based on the mass of the tablet (chlorinated isocyanuric acid composition).

[0021] As excipients, known excipients can be used, such as sodium sulfate, sodium chloride, as well as alkali metal silicates, carbonates, bicarbonates, phosphates, sulfates, etc. As a solvent adjusting agent, known solvent adjusting agents can be used, such as succinic acid, fumaric acid, phthalic acid, potassium sulfate, and benzoic acid. The binder is not particularly limited as long as it has the function of binding solid particles and is preferably water-soluble, but examples include carboxymethylcellulose, sodium carboxymethylcellulose, dextrin, polyethylene glycol, polyvinyl alcohol, polyalkylene glycol, lignin sulfonate, gum arabic, starches, and sucrose.

[0022] Furthermore, the chlorinated isocyanuric acid composition of the present invention can be used in any form, such as powder, granules, or tablets, depending on the application. Tablets are particularly preferred. Powders and granules have a large surface area and are therefore prone to absorbing moisture, and may also produce an irritating odor due to powdering, so care must be taken during use. The method of blending a chlorinated isocyanuric acid compound with magnesium sulfate, alkali carbonate, optionally a non-halogenated cyclic urea compound, and other components is not particularly limited, as long as these powders can be uniformly mixed.

[0023] Tablets can be manufactured by known methods, such as filling a mold with a powdered or granular chlorinated isocyanuric acid composition and applying pressure (hereinafter also referred to as "tableting"). When manufactured industrially, a known pressurized tablet press consisting of a mold (punch) and a pressurizing device is preferably used. The shape of the tablets is not particularly limited, and the shape can be determined as appropriate from the standpoint of ease of compression and ease of handling and use. Examples include cylindrical, cubic, rectangular, spherical, and donut shapes.

[0024] The amount of chlorinated isocyanuric acid compound in the tablet is preferably 95% or more based on the total mass of the tablet. Furthermore, when forming chlorinated isocyanuric acid compounds into tablets, the amount of magnesium sulfate is preferably 0.01 to 0.4% by mass based on 100% by mass of the chlorinated isocyanuric acid compound, and the amount of alkali carbonate is preferably 0.1 to 0.3% by mass. If the amounts of magnesium sulfate and alkali carbonate are within the above range, the preservation / storage period This prevents the tablets from disintegrating and suppresses the generation of chlorine gas. If the amount of alkali carbonate exceeds 0.3% by mass, the tablets may absorb moisture and generate carbon dioxide when placed under high humidity conditions, potentially causing them to disintegrate.

[0025] The size of the tablets can be adjusted as appropriate depending on the intended use. For example, tablets with a diameter of 1-8 cm and a thickness of 0.5-5 cm are common, but are not limited to these dimensions. The density of the tablets is 1.70 to 1.95 g / cm³. 3 A density of 1.70 g / cm³ is preferred. 3 If the value is lower than 1.95 g / cm³, the tablets are prone to breaking down during handling or transport. 3 If it exceeds this value, a high compression pressure is required for molding, thus requiring excessive energy. [Examples]

[0026] The chlorinated isocyanuric acid composition and the tablets formed therefrom of the present invention will be described in more detail below, but the present invention is not limited in any way to the following examples.

[0027] (Example 1) A powdered trichloroisocyanuric acid composition was obtained by mixing 100.00 g of trichloroisocyanuric acid (manufactured by Nissan Chemical Corporation), 0.18 g of magnesium stearate (manufactured by NOF Corporation), 0.10 g of anhydrous magnesium sulfate (manufactured by Tomita Pharmaceutical Co., Ltd.), and 0.50 g of sodium carbonate (manufactured by Takasugi Pharmaceutical Co., Ltd.). 30 g of the obtained trichloroisocyanuric acid composition was filled into a mold (inner diameter 35 mm) of a press machine (manufactured by NPa Systems Co., Ltd., model number TB-200H-V11), and compressed under pressure to a height of 18 mm to obtain cylindrical tablets. The press pressure used to manufacture the tablets was 420-530 kg / cm². 2 That was the case.

[0028] (Examples 2 to 10, Comparative Examples 1 to 6) Tablets were prepared in the same manner as in Example 1, except that the amounts of trichloroisocyanuric acid (TCCA), magnesium stearate (MgSt), anhydrous magnesium sulfate (MgSO4), anhydrous sodium carbonate (Na2CO3), and cyanuric acid (CA: manufactured by Nissan Chemical Corporation) were changed to the amounts shown in Tables 1 and 2 below.

[0029] (Storage stability test) The tablets from Example 1 were placed in a polypropylene bag permeable to moisture and chlorine gas and sealed by heat sealing. The polypropylene bag containing the tablets was placed in a 900 mL glass bottle, the lid of the glass bottle was closed, and the bottle was left standing in a constant temperature and humidity chamber at 30°C and 75% RH. The chlorine gas concentration in the glass bottle was measured 1, 3, 5, 7, 14, 21, 28, 35, 42, and 49 days after standing, using a chlorine detection tube (No. 8H) manufactured by Gastec Co., Ltd. The measurement results are shown in Table 1 below. The chlorine gas concentration was similarly measured for the tablets of Examples 2 to 10 and Comparative Examples 1 to 6. Tablets with a chlorine gas concentration of 5 ppm or less after 7 days, 50 ppm or less after 14 days, and 1000 ppm or less after 28 days were considered to have good stability, while those exceeding these levels were considered to have poor stability. The measured chlorine gas concentrations and evaluation results are shown in Tables 1 and 2 below.

[0030] [Table 1] [Table 2]

[0031] Tables 1 and 2 show that the tablets of Examples 1 to 6, which were pressure-molded from a trichloroisocyanuric acid composition containing anhydrous magnesium sulfate and sodium carbonate, exhibited suppressed generation of chlorine-based gases, which are decomposition products of trichloroisocyanuric acid, and improved storage stability compared to the tablets of Comparative Example 1, which were pressure-molded from trichloroisocyanuric acid, and the tablets of Comparative Examples 2 to 6, which were pressure-molded from a trichloroisocyanuric acid composition containing anhydrous magnesium sulfate, sodium carbonate, or cyanuric acid.

[0032] (Examples 11 to 14) Tablets were prepared in the same manner as in Example 1, except that the amounts of trichloroisocyanuric acid, magnesium stearate, anhydrous magnesium sulfate, anhydrous sodium carbonate, and cyanuric acid were changed to the amounts shown in Table 3 below. The prepared tablets were tested in the same manner as the storage stability test described above, and the concentration of chlorine gas generated was measured to evaluate their stability. The measurement results are shown in Table 3.

[0033] (Tablet disintegration test) The tablet disintegration test method will be explained based on Figure 1. A polyvinyl chloride cylinder 2 with an inner diameter of 40 mm and a length of 20 cm was prepared, and four notches 3 measuring approximately 25 mm in length and 10 mm in width were made at one end. Ten tablets 1 were stacked inside the cylinder 2, and lids were placed on both ends of the cylinder. A cylindrical tube was placed upright and fixed in a tank with a water depth of 2 cm and 40°C warm water flowing through it, with the notched portion 3 facing downwards, and left undisturbed for 7 days (168 hours). After 7 days (168 hours), the tablet was removed from cylinder 2 and its shape was visually observed. Tablets that showed no cracking or disintegration were classified as "no disintegration," while tablets that showed cracking or disintegration in even one tablet were classified as "disintegrated." The evaluation results are shown in Table 3.

[0034] [Table 3]

[0035] Table 3 shows that the tablets of Examples 11 to 13, which were pressure-molded from a trichloroisocyanuric acid composition containing anhydrous magnesium sulfate and sodium carbonate, suppressed the generation of chlorine gas compared to the tablets of Comparative Examples 1 to 6. Furthermore, it was confirmed that the tablets did not disintegrate even under high temperature and high humidity conditions.

Claims

1. A chlorinated isocyanuric acid composition, The compound is a chlorinated isocyanuric acid compound blended with magnesium sulfate, alkali carbonate, and a non-halogenated cyclic urea compound, and Based on the total mass of the chlorinated isocyanuric acid composition, the amount of the chlorinated isocyanuric acid compound is 95% by mass or more. A chlorinated isocyanuric acid composition characterized by the following.

2. The chlorinated isocyanuric acid composition according to claim 1, wherein the alkali carbonate salt is sodium carbonate.

3. The chlorinated isocyanuric acid composition according to claim 1, wherein the non-halogenated cyclic urea compound is cyanuric acid.

4. The chlorinated isocyanuric acid composition according to claim 1 or claim 2, wherein the chlorinated isocyanuric acid compound is trichloroisocyanuric acid.

5. The chlorinated isocyanuric acid composition according to claim 1 or claim 2, wherein the amount of magnesium sulfate is 0.01 to 0.4 parts by mass and the amount of alkali carbonate is 0.1 to 1.0 parts by mass per 100 parts by mass of the chlorinated isocyanuric acid compound.

6. The chlorinated isocyanuric acid composition according to claim 5, wherein the amount of alkali carbonate salt blended is 0.1 to 0.3 parts by mass per 100 parts by mass of the chlorinated isocyanuric acid compound.

7. The chlorinated isocyanuric acid composition according to claim 1, wherein the amount of the non-halogenated cyclic urea compound blended is 0.01 to 1.0 parts by mass per 100 parts by mass of the chlorinated isocyanuric acid compound.

8. The chlorinated isocyanuric acid composition according to claim 1, wherein the amount of the non-halogenated cyclic urea compound blended is 0.01 to 0.2 parts by mass per 100 parts by mass of the chlorinated isocyanuric acid compound.

9. A tablet which is a pressure-molded body of a chlorinated isocyanuric acid composition comprising a chlorinated isocyanuric acid compound, magnesium sulfate, alkali carbonate salt, and a non-halogenated cyclic urea compound, Based on the mass of the chlorinated isocyanuric acid compound, the amount of magnesium sulfate is 0.01 to 0.4% by mass, the amount of alkali carbonate is 0.1 to 0.3% by mass, and the amount of non-halogenated cyclic urea compound is 0.01 to 0.2% by mass. Based on the total mass of the tablet, the amount of the chlorinated isocyanuric acid compound is 95% by mass or more, and the sum of the amounts of the chlorinated isocyanuric acid compound, magnesium sulfate, alkali carbonate salt, and non-halogenated cyclic urea compound is 100% by mass or less. tablet.

10. The tablet according to claim 9, wherein the alkali carbonate salt is sodium carbonate.

11. The tablet according to claim 9, wherein the chlorinated isocyanuric acid compound is trichloroisocyanuric acid.

12. The tablet according to claim 9, wherein the non-halogenated cyclic urea compound is cyanuric acid.

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