Composition and use thereof

Abstract

The present invention provides a solid composition containing an oxygen-based oxidizing agent and a halogen-based oxidizing agent, the composition being useful for water treatment or other such applications and having exceptional safety during use and stability during storage. The present invention relates to: a solid composition containing a halogen-based oxidizing agent and an oxygen-based oxidizing agent, wherein either or both of the halogen-based oxidizing agent and the oxygen-based oxidizing agent are coated with a coating layer; a method for producing the composition; and a method for using the composition.

Description

Composition and its use

[0001] The present invention relates to compositions and methods of use that can be used in applications such as treating a wide variety of bodies of water, such as pools, spas, fountains, and the like.

[0002] A known technique is to use a combination of a halogen-based oxidizer (e.g., chlorine) and an oxygen-based oxidizer (e.g., peroxysulfate) as a shock agent when the water quality in a pool deteriorates significantly, such as when the water becomes cloudy or algae grow.

[0003] For example, Patent Document 1 discloses a technique for removing volatile halogen compounds from the air and water of an indoor water facility, in which a halogen source (including sodium dichloroisocyanurate, a halogen-based oxidizing agent), a coagulant, and a peroxygen compound (including potassium monopersulfate, an oxygen-based oxidizing agent) are added separately while monitoring the oxidation-reduction potential of the water area. However, the method of adding the halogen source and the peroxygen compound separately has the problem of being time-consuming to perform the treatment.

[0004] Patent Document 2 discloses a solid composition useful for water treatment in circulating water systems for recreational, ornamental, and industrial water applications. The solid composition contains an oxidizing agent and an active halogen agent, and the oxidizing agent is potassium monopersulfate (an oxygen-based oxidizing agent), and the active halogen agent is an alkali metal salt of dichloroisocyanuric acid (a halogen-based oxidizing agent), a halogenated dimethylhydantoin (a halogen-based oxidizing agent), or a mixture thereof. The solid composition is described as being safe and stable, with little generation of toxic chlorine gas and heat generation when in contact with water.

[0005] Patent Document 3 discloses a solid bleach-containing product having a coating layer and a composition incorporating the same, and describes that the composition is stabilized by protecting the solid bleach from deterioration, inactivation, and decomposition.

[0006] U.S. Patent No. 6,409,926 U.S. Patent Publication No. 2006 / 0078584 International Publication No. 2017 / 183726

[0007] However, because the solid composition described in Patent Document 2 contains an oxidizing agent (oxygen-based oxidizing agent) and an active halogen agent (halogen-based oxidizing agent), there is a possibility that problems such as heat generation due to unexpected moisture contamination during use, significantly compromising safety, and reduced stability during long-term storage may occur. The inventors investigated this issue and found that the solid composition described in Patent Document 2, which is a mixture of an oxidizing agent and an active halogen agent, generates heat upon contact with a small amount of water, resulting in high temperatures and being dangerous, and that gas generation due to side reactions, corrosion of storage containers caused by the generated gas, and damage due to corrosion, were observed during storage. In other words, it was confirmed that the solid composition described in Patent Document 2 has safety and stability problems during use and storage.

[0008] Therefore, an object of the present invention is to provide a composition containing an oxygen-based oxidizing agent and a halogen-based oxidizing agent, which is useful for various applications such as water treatment, and is also highly safe during use and stable during storage, as well as a method for using the composition.

[0009] As a result of intensive research into solving the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by a solid composition containing a halogen-based oxidizing agent and an oxygen-based oxidizing agent, in which either or both of the halogen-based oxidizing agent and the oxygen-based oxidizing agent are coated with a coating layer.Further research has led to the completion of the present invention.

[0010] That is, the present invention provides the following compositions, methods for producing the same, and uses (methods of using the compositions): [1] A composition containing a halogen-based oxidizing agent and an oxygen-based oxidizing agent, wherein either or both of the halogen-based oxidizing agent and the oxygen-based oxidizing agent are coated with a coating layer. [2] The composition according to [1], which is one composition selected from the group consisting of the following (1) to (3): (1) a composition containing a halogen-based oxidizing agent and a halogen-based oxidizing agent-containing substance having a coating layer coating its surface, and an oxygen-based oxidizing agent, (2) an oxygen-based oxidizing agent and an oxygen-based oxidizing agent-containing substance having a coating layer coating its surface, and a composition containing a halogen-based oxidizing agent, and (3) a composition containing a halogen-based oxidizing agent and a halogen-based oxidizing agent-containing substance having a coating layer coating its surface, and an oxygen-based oxidizing agent-containing substance having a coating layer coating its surface. [3] The composition according to [1] or [2], wherein the coating layer contains one or more selected from the group consisting of a metal salt of a carboxylic acid, a surfactant, a polysaccharide, a higher fatty acid, a paraffin wax, a zeolite, and a resin. [4] The composition according to [3], wherein the coating layer contains a metal salt of a carboxylic acid, and the metal salt of the carboxylic acid is one or more selected from the group consisting of an alkali metal salt of an aromatic carboxylic acid, an alkali metal salt of an acyclic dicarboxylic acid, an alkali metal salt of an acyclic monocarboxylic acid, and a mixture thereof. [5] The composition according to any one of [1] to [4], wherein the composition further contains a flocculant (particularly, a cationic polymer flocculant having a quaternary ammonium salt). [6] The composition according to any one of [1] to [5], wherein the composition is a composition containing a halogen-based oxidizing agent and a halogen-based oxidizing agent-containing substance having a coating layer covering the surface of the halogen-based oxidizing agent, and an oxygen-based oxidizing agent (the composition (1) of [2]). [7] The composition according to [6], wherein the content of the halogen-based oxidizing agent-containing substance in the composition is 5% by weight or more and 95% by weight or less. [8] The composition according to [6] or [7], wherein the content of the halogen-based oxidizing agent in the halogen-based oxidizing agent-containing material is 30% by weight or more and 95% by weight or less. [9] The composition according to any one of [6] to [8], wherein the content of the oxygen-based oxidizing agent in the composition is 5% by weight or more and 95% by weight or less.

[10] A method for producing the composition according to [6] above, comprising a step of mixing a halogen-based oxidizing agent, a halogen-based oxidizing agent-containing composition having a coating layer covering its surface, and an oxygen-based oxidizing agent.

[11] A method for producing the composition according to

[10] above, comprising a step of contacting a coating liquid with the surface of a halogen-based oxidizing agent to produce a halogen-based oxidizing agent-containing composition.

[12] The composition according to any one of [1] to [5], wherein the composition contains a halogen-based oxidizing agent, a halogen-based oxidizing agent-containing composition having a coating layer covering its surface, and an oxygen-based oxidizing agent, a halogen-based oxidizing agent-containing composition having a coating layer covering its surface (the composition of (3) of [2]).

[13] The composition according to

[12] , wherein the content of the halogen-based oxidizing agent-containing composition in the composition is 5% by weight or more and 95% by weight or less.

[14] The composition according to

[12] or

[13] , wherein the content of the halogen-based oxidizing agent in the halogen-based oxidizing agent-containing composition is 30% by weight or more and 95% by weight or less.

[15] The composition according to any one of

[12] to

[14] , wherein the content of the oxygen-based oxidant-containing substance in the composition is 5% by weight or more and 95% by weight or less.

[16] The composition according to any one of

[12] to

[15] , wherein the content of the oxygen-based oxidant in the oxygen-based oxidant-containing substance is 30% by weight or more and 95% by weight or less.

[17] A method for producing the composition according to

[12] , comprising a step of mixing a halogen-based oxidant-containing substance having a halogen-based oxidant and a coating layer covering its surface, and an oxygen-based oxidant and an oxygen-based oxidant-containing substance having a coating layer covering its surface.

[18] The method according to

[17] , comprising a step of contacting the surface of the oxygen-based oxidant with a coating liquid to produce an oxygen-based oxidant-containing substance.

[19] A method for treating a water body, comprising a step of applying (contacting) the composition according to any one of [1] to [9] and

[12] to

[16] to the water body.

[20] A method for treating pulp, comprising a step of contacting pulp with the composition according to any one of [1] to [9] and

[12] to

[16] .

[0011] The composition of the present invention contains a halogen-based oxidizing agent and an oxygen-based oxidizing agent, with either or both of the halogen-based oxidizing agent and the oxygen-based oxidizing agent coated with a coating layer. The composition maintains high water treatment capacity while exhibiting excellent safety during use and stability during storage. Specifically, the composition has effects such as reducing turbidity in target water bodies and removing organic matter during use. When water is added to the composition, heat generation is suppressed, preventing the composition from reaching high temperatures. Furthermore, gas generation due to side reactions is suppressed during storage, thereby preventing swelling and damage to packaging containers caused by the gas generated. Furthermore, heat generation or decomposition can be suppressed even if water is unintentionally added to the composition during production or use, allowing for safe production and use.

[0012] As used herein, "suppressing heat generation" means that when a predetermined amount of water is added to a composition, the maximum temperature rise due to heat generation of the composition is lower than that of a comparison object, and / or when a predetermined amount of water is added to a composition, the time from the addition of water to the maximum temperature rise due to heat generation of the composition is longer than that of a comparison object. "Suppressing swelling of a packaging container" means that when a composition is sealed in a predetermined packaging container, the increase in volume of the packaging container is smaller than that of a comparison object. "Suppressing damage to a packaging container" means that the degree of damage to the packaging container is less than that of a comparison object.

[0013] 1 shows the results of a temperature change test due to moisture contamination in Test Example 1. 2 shows the results of a temperature change test due to moisture contamination in Test Example 1. 3 shows the results of a temperature change test due to moisture contamination in Test Example 3. 4 shows the results of a temperature change test due to moisture contamination in Test Example 4. 5 shows the results of a temperature change test due to moisture contamination in Test Example 5. 6 shows the results of a temperature change test due to moisture contamination in Test Example 6. 7 shows the results of a storage stability test (storage at 40°C / 75% RH / 1 month) of a 460g aluminum pouch packaged product (Comparative Example 14) in Test Example 7. (1) shows corrosion on the side of the aluminum pouch package, and (2) shows corrosion on the bottom of the aluminum pouch package. 8 shows the results of a storage stability test (storage at 40°C / 75% RH / 1.5 months) of a 460g aluminum pouch packaged product (Comparative Example 14) in Test Example 7. (1) shows corrosion on the side of the aluminum pouch packaging, and (2) shows corrosion on the bottom of the aluminum pouch packaging. The results of a storage stability test (storage at 50°C / 30% RH / 2 months) of the 460 g aluminum pouch packaged product (Comparative Example 14) in Test Example 7 are shown. Corrosion on the bottom of the aluminum pouch packaging is shown.

[0014] (Composition) The composition of the present invention is characterized by containing a halogen-based oxidizing agent and an oxygen-based oxidizing agent, and one or both of the halogen-based oxidizing agent and the oxygen-based oxidizing agent are coated with a coating layer. Examples of this composition include the following embodiments (1) to (3): (1) a composition containing a halogen-based oxidizing agent and a halogen-based oxidizing agent-containing substance having a coating layer coating its surface, and an oxygen-based oxidizing agent; (2) a composition containing an oxygen-based oxidizing agent and an oxygen-based oxidizing agent-containing substance having a coating layer coating its surface, and a halogen-based oxidizing agent; and (3) a composition containing a halogen-based oxidizing agent and a halogen-based oxidizing agent-containing substance having a coating layer coating its surface, and an oxygen-based oxidizing agent and an oxygen-based oxidizing agent-containing substance having a coating layer coating its surface. Of these, compositions (1) and (3) are preferred, and composition (1) is more preferred.

[0015] The halogen-based oxidizing agent, the halogen-based oxidizing agent-containing substance having a coating layer, the oxygen-based oxidizing agent, and the oxygen-based oxidizing agent-containing substance having a coating layer that can be contained in the composition of the present invention will be described below.

[0016] (Halogen-Based Oxidizing Agent) The halogen-based oxidizing agent is a compound that dissolves in water to generate a free halogen (hypohalous acid such as hypochlorous acid, hypohalous acid ion, molecular halogen such as chlorine), and examples thereof include one or more selected from the group consisting of halogenated isocyanuric acid, alkali metal salts of halogenated isocyanuric acid, hydrates of alkali metal salts of halogenated isocyanuric acid, halogenated hydantoin, metal hypochlorite, and mixtures thereof.

[0017] The halogenated isocyanuric acid, alkali metal salt of halogenated isocyanuric acid, and hydrate of alkali metal salt of halogenated isocyanuric acid are preferably at least one selected from the group consisting of trichloroisocyanuric acid, sodium dichloroisocyanurate, hydrate of sodium dichloroisocyanurate, potassium dichloroisocyanurate, and mixtures thereof. From the viewpoints of availability and safety, more preferably at least one selected from the group consisting of trichloroisocyanuric acid, sodium dichloroisocyanurate, hydrate of sodium dichloroisocyanurate, and mixtures thereof.

[0018] The halogenated hydantoin is preferably one or more selected from the group consisting of 1,3-dichloro-5,5-dimethylhydantoin, 1-bromo-3-chloro-5,5-dimethylhydantoin, 1-chloro-3-bromo-5,5-dimethylhydantoin, 1,3-dibromo-5,5-dimethylhydantoin, 1,3-dichloro-5,5-ethylmethylhydantoin, and mixtures thereof. Note that 1-bromo-3-chloro-5,5-dimethylhydantoin and 1-chloro-3-bromo-5,5-dimethylhydantoin may be collectively referred to as bromochloro-5,5-dimethylhydantoin.

[0019] As the metal hypochlorite, calcium hypochlorite (bleaching powder) is preferred.

[0020] The halogen-based oxidizing agent is a solid and can take the form of, for example, powder, granules, tablets, etc. Powder is preferred. These forms can be prepared by known methods. The average particle size of the halogen-based oxidizing agent is usually 1 to 5,000 μm, preferably 10 to 3,000 μm, and more preferably 50 to 2,000 μm. This average particle size can be measured in accordance with the measurement method for "average particle size of composition" described below.

[0021] When the halogen-based oxidizing agent is a chlorine-based oxidizing agent, its available chlorine content (Cl ２ The effective chlorine content (equivalent value) can be calculated using iodometric titration. That is, the iodine liberated by the reaction of active chlorine with potassium iodide is titrated with an aqueous sodium thiosulfate solution, and the effective chlorine content is calculated using the following formula 1:

[0022] Available chlorine content (%) = a × f × 0.35452 / b (Formula 1) a: 0.1 N sodium thiosulfate aqueous solution required for titration (ml) b: sample (g) f: factor of 0.1 N sodium thiosulfate aqueous solution

[0023] The theoretical available chlorine content of trichloroisocyanuric acid is 91.5%, that of sodium dichloroisocyanurate is 64.5%, and that of sodium dichloroisocyanurate dihydrate is 55.4%.

[0024] Halogen-based oxidizing agents are commercially available, and for example, sodium dichloroisocyanurate and sodium trichloroisocyanurate are readily available from Shikoku Chemicals Corporation under the trade name Neochlor (registered trademark).

[0025] The content of the halogen-based oxidizing agent in the composition of the present invention is usually 5 to 95% by weight, preferably 8 to 90% by weight, more preferably 10 to 80% by weight, and particularly preferably 10 to 70% by weight.

[0026] (Halogen-based oxidizing agent-containing material having a coating layer) The halogen-based oxidizing agent-containing material has a structure in which the surface of a solid halogen-based oxidizing agent is covered with a coating layer. That is, the surface of the halogen-based oxidizing agent such as particles, granules, tablets, etc. is protected by a coating layer. The halogen-based oxidizing agent used here can be one described above.

[0027] The compound used for the coating layer is not particularly limited as long as it is a compound that can coat the surface of the halogen-based oxidizing agent and suppress the interaction between the halogen-based oxidizing agent and the oxygen-based oxidizing agent and other components.

[0028] Examples of compounds that can be used as the coating layer include metal salts of carboxylic acids, surfactants, polysaccharides, higher fatty acids, paraffin wax, zeolites, and resins. These compounds may be used alone or in combination of two or more compounds. In an embodiment where two or more compounds are used in combination, two or more compounds may be mixed to form a coating layer containing multiple compounds, or a multilayer structure may be formed by forming a coating layer with one compound and then forming a further coating layer with another compound.

[0029] The phrase "the halogen-based oxidizing agent is coated with a coating layer" means that the halogen-based oxidizing agent is completely or incompletely coated with a coating layer within a range that does not impair the effects of the present invention. Specifically, this includes both a case where the entire halogen-based oxidizing agent is coated with a coating layer and a case where only a part of the halogen-based oxidizing agent is coated. It also includes a case where the surface of each halogen-based oxidizing agent in the form of powder or the like is completely coated with a coating layer and a case where the surface is only a part of the coating layer.

[0030] Among compounds that can be used for the coating layer, metal salts of carboxylic acids are preferred because they have good solubility in water and excellent stability against halogen-based oxidizing agents. In addition, they are easy to process as a coating layer, have excellent protection against halogen-based oxidizing agents as a coating layer, and are easy to obtain and handle.

[0031] Examples of the metal salt of carboxylic acid include one or more selected from the group consisting of metal salts of aromatic carboxylic acids, metal salts of acyclic dicarboxylic acids, metal salts of acyclic monocarboxylic acids, metal salts of other carboxylic acids, and mixtures thereof. The metal salt of carboxylic acid may be a carboxylic acid in which the carboxyl group of the carboxylic acid has been completely neutralized as a metal salt, or a carboxylic acid in which the carboxyl group has been partially neutralized as a metal salt, or may contain a carboxylic acid that has not been converted into a metal salt. By using a metal salt of carboxylic acid, the halogen-based oxidizing agent-containing material having a coating layer and a composition containing the same can be stabilized by protecting the halogen-based oxidizing agent from deterioration, deactivation, and decomposition, and can effectively suppress the interaction between the halogen-based oxidizing agent and oxygen-based oxidizing agents, etc.

[0032] Furthermore, a coating layer formed containing a metal salt of carboxylic acid is stable even when in contact with a halogen-based oxidizing agent, and no undesirable side reactions occur between the halogen-based oxidizing agent and the coating layer. Therefore, there is no need to provide a separate layer to isolate the halogen-based oxidizing agent from the coating layer, and the coating layer can be directly formed on the surface of the halogen-based oxidizing agent. In addition, a coating layer containing a metal salt of carboxylic acid is preferred because it is less likely to agglomerate and has excellent processability. Similarly, a coating layer can be directly formed on the surface of an oxygen-based oxidizing agent.

[0033] The metal salt of an aromatic carboxylic acid refers to a metal salt of a compound having an aromatic ring and a carboxyl group in its structure. The metal salt of an aromatic carboxylic acid is preferably one or more selected from the group consisting of metal salts of benzoic acid, phthalic acid (ortho-form), isophthalic acid (meta-form), terephthalic acid (para-form), trimellitic acid, and para-t-butylbenzoic acid, and mixtures thereof. Examples of the metal salt include alkali metal salts such as lithium salt, sodium salt, and potassium salt, and alkaline earth metal salts such as calcium salt and magnesium salt. Alkali metal salts are preferred from the viewpoint of ease of availability, and sodium salts and potassium salts are even more preferred from the viewpoint of solubility in water. The metal salt of an aromatic carboxylic acid is particularly preferably one or more selected from the group consisting of alkali metal salts of benzoic acid, alkali metal salts of para-t-butylbenzoic acid, and mixtures thereof. Sodium benzoate is preferred as the alkali metal salt of benzoic acid, and sodium para-t-butylbenzoate is preferred as the alkali metal salt of para-t-butylbenzoic acid.

[0034] The metal salt of an acyclic dicarboxylic acid refers to a metal salt of a compound that does not have a cyclic structure within its structure and has two carboxyl groups. Examples of the metal salt of an acyclic dicarboxylic acid include, for example, one or more selected from the group consisting of metal salts of oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, D-tartaric acid, L-tartaric acid, D-malic acid, L-malic acid, D-aspartic acid, L-aspartic acid, glutaric acid, D-glutamic acid, L-glutamic acid, itaconic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, and tetradecanedioic acid, and mixtures thereof. Examples of the metal salt include alkali metal salts such as lithium salt, sodium salt, and potassium salt, and alkaline earth metal salts such as calcium salt and magnesium salt. Alkali metal salts are preferred from the viewpoint of availability, and sodium salts and potassium salts are more preferred from the viewpoint of solubility in water. The metal salt of acyclic dicarboxylic acid is more preferably at least one selected from the group consisting of alkali metal salts of adipic acid, alkali metal salts of sebacic acid, alkali metal salts of undecanedioic acid, alkali metal salts of dodecanedioic acid, and mixtures thereof. Disodium adipate is suitable as the alkali metal salt of adipic acid, disodium sebacic acid is suitable as the alkali metal salt of sebacic acid, disodium undecanedioate is suitable as the alkali metal salt of undecanedioic acid, and disodium dodecanedioate is suitable as the alkali metal salt of dodecanedioic acid.

[0035] The term "metal salt of acyclic monocarboxylic acid" refers to a metal salt of a compound having one carboxyl group and no cyclic structure in its structure. Examples of metal salts of acyclic monocarboxylic acids include, for example, one or more selected from the group consisting of metal salts of formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid (caproic acid), heptanoic acid (enanthic acid), octanoic acid, nonanoic acid, decanoic acid, dodecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, oleic acid, linoleic acid, linolenic acid, acrylic acid, methacrylic acid, isobutyric acid, and isovaleric acid, and mixtures thereof. Metal salts include, for example, alkali metal salts such as lithium salt, sodium salt, and potassium salt, and alkaline earth metal salts such as calcium salt and magnesium salt. Alkali metal salts are preferred from the viewpoint of availability, and sodium salts and potassium salts are more preferred from the viewpoint of solubility in water. The metal salt of acyclic monocarboxylic acid is more preferably at least one selected from the group consisting of alkali metal salts of heptanoic acid (enanthic acid), alkali metal salts of octanoic acid, alkali metal salts of nonanoic acid, alkali metal salts of decanoic acid, alkali metal salts of dodecanoic acid, alkali metal salts of lauric acid, alkali metal salts of myristic acid, alkali metal salts of palmitic acid, alkali metal salts of stearic acid, and mixtures thereof. As an alkali metal salt of heptanoic acid (enanthic acid), sodium heptanoate is preferred, as an alkali metal salt of octanoic acid, sodium octanoate is preferred, as an alkali metal salt of nonanoic acid, sodium nonanoate is preferred, as an alkali metal salt of decanoic acid, sodium decanoate is preferred, as an alkali metal salt of dodecanoic acid, sodium dodecanoate is preferred, as an alkali metal salt of lauric acid, sodium myristate is preferred, as an alkali metal salt of myristic acid, sodium palmitate is preferred, and as an alkali metal salt of stearic acid, sodium stearate is preferred. Among the above, from the viewpoint of effective heat suppression, alkali metal salts of acyclic monocarboxylic acids having 7 to 20 carbon atoms, such as heptanoic acid, octanoic acid, and decanoic acid, are preferred.

[0036] The metal salt of other carboxylic acids refers to a metal salt of a compound which may have a cyclic structure in the compound structure and has three or more carboxyl groups. As the metal salt of other carboxylic acids, for example, a metal salt of citric acid is preferred. Examples of the metal salt include alkali metal salts such as lithium salt, sodium salt, potassium salt, and alkaline earth metal salts such as calcium salt. From the viewpoint of availability, alkali metal salts are preferred, and from the viewpoint of solubility in water, sodium salt and potassium salt are more preferred. As the alkali metal salt of citric acid, trisodium citrate is suitable.

[0037] The metal salts of carboxylic acids, which are components that can be contained in the coating layer, i.e., metal salts of aromatic carboxylic acids, metal salts of acyclic dicarboxylic acids, metal salts of acyclic monocarboxylic acids, and metal salts of other carboxylic acids, may be used alone or in combination of two or more compounds.

[0038] The content of the halogen-based oxidizing agent-containing substance having a coating layer in the composition of the present invention is usually 5 to 95% by weight, preferably 8 to 92% by weight, more preferably 10 to 80% by weight, and particularly preferably 10 to 70% by weight.

[0039] From the viewpoint of facilitating the formation of a coating layer on the surface of a solid halogen-based oxidizing agent, the content of the metal salt of carboxylic acid contained in the coating layer in the halogen-based oxidizing agent-containing material is preferably 30% by weight or more, more preferably 50% by weight or more, and even more preferably 70% by weight or more, when the total weight of the coating layer is taken as 100% by weight.

[0040] The coating layer may contain various compounds such as inorganic and organic substances, as long as the effects of the present invention are not impaired. Examples of inorganic substances include, but are not limited to, phosphates, sulfates, silicates, chlorides, iodides, bromides, etc. Examples of organic substances include, but are not limited to, polysaccharides, polymeric compounds, and salts of organic substances.

[0041] The proportion (wt%) of the coating layer in a halogen-based oxidizing agent-containing material having a coating layer, when the total weight of the halogen-based oxidizing agent-containing material is taken as 100 wt%, is preferably 5 wt% or more, more preferably 10 wt% or more, and even more preferably 15 wt% or more as a lower limit from the viewpoint of effectively suppressing the interaction between the halogen-based oxidizing agent and other components by the coating layer. Also, from the viewpoint of exerting the above-mentioned effect without an excessive proportion of the coating layer, the upper limit is preferably 70 wt% or less, more preferably 50 wt% or less, and even more preferably 45 wt% or less.

[0042] The proportion (wt%) of the halogen-based oxidizing agent in the halogen-based oxidizing agent-containing material, when the total weight of the halogen-based oxidizing agent-containing material is taken as 100 wt%, is preferably 30 wt% or more as a lower limit, more preferably 50 wt% or more, and even more preferably 55 wt% or more, and is preferably 95 wt% or less as an upper limit, more preferably 90 wt% or less, and even more preferably 85 wt% or less.

[0043] When the halogen-based oxidizing agent is a chlorine-based oxidizing agent, the ratio of the coating layer in the chlorine-based oxidizing agent-containing material having the coating layer can be calculated by the following calculation method using Equation 2.

[0044] Ratio of coating layer (wt %)=Q1×100 / Q2 (Formula 2) Q1: weight (g) of the coating layer in the chlorine-based oxidizing agent-containing material having the coating layer Q2: weight (g) of the chlorine-based oxidizing agent-containing material having the coating layer

[0045] For example, if 1 g of a chlorine-based oxidizing agent-containing material having a coating layer contains 0.3 g of the coating layer, the proportion (wt %) of the coating layer is calculated as 0.3 × 100 / 1 = 30, or 30 wt %, according to Equation 2. The weight of the coating layer in a chlorine-based oxidizing agent-containing material having a coating layer can be determined by, for example, dissolving the chlorine-based oxidizing agent-containing material having a coating layer in a solvent such as water and analyzing the solution using a known analytical method such as liquid chromatography to quantify the weight of the compound used in the coating layer, or by subtracting the weight of the chlorine-based oxidizing agent from the weight of the chlorine-based oxidizing agent-containing material having a coating layer. The weight of the chlorine-based oxidizing agent can also be determined using a known analytical method such as liquid chromatography.

[0046] The identification and quantification of the coating layer can be measured by a known method. For example, when the absorbance of the compound used in the coating layer is known, the proportion (wt%) of the coating layer can be calculated by a method (absorbance method) in which the compound used in the coating layer is adjusted to a known concentration and a calibration curve is prepared, or the measurement can be performed using a widely known method such as liquid chromatography or gas chromatography. When it is easier to quantify the halogen-based oxidizing agent than the coating layer, the weight of the coating layer can be calculated from the weight of the halogen-based oxidizing agent.

[0047] When the halogen-based oxidizing agent is a chlorine-based oxidizing agent, the proportion of the coating layer can be calculated from the available chlorine content of the chlorine-based oxidizing agent-containing material using the following formula 3. In this case, when the chlorine-based oxidizing agent-containing material having a coating layer contains components other than the coating layer, such as moisture, the proportion of the coating layer can be obtained by subtracting the moisture content (or the content of components other than the coating layer) (wt %) from the calculation result.

[0048] Ratio of coating layer (wt%)=(P1-P2)×100 / P1 (Formula 3) P1: Available chlorine content (%) of the chlorine-based oxidizing agent used as raw material P2: Available chlorine content (%) of the chlorine-based oxidizing agent-containing material having a coating layer

[0049] That is, for example, when a chlorine-based oxidizing agent-containing substance having a coating layer is prepared using sodium dichloroisocyanurate having an available chlorine content of 64.5% as a chlorine-based oxidizing agent, and the available chlorine content of the chlorine-based oxidizing agent-containing substance having a coating layer is 40.0%, the proportion of the coating layer is calculated to be 38.0% from Equation 3.

[0050] The content of the metal salt of carboxylic acid contained in the coating layer of the chlorine-based oxidizing agent-containing material having a coating layer may be quantified using a known analytical method such as liquid chromatography. For example, if the content of the metal salt of carboxylic acid in the chlorine-based oxidizing agent-containing material having a coating layer is 5% by weight and the proportion of the coating layer in the chlorine-based oxidizing agent-containing material having a coating layer is 30% by weight, the content of the metal salt of carboxylic acid contained in the coating layer is calculated to be 16.7% by weight when the total weight of the coating layer is 100% by weight.

[0051] The method for quantifying the proportion of the coating layer in the halogen-based oxidizing agent-containing material having a coating layer and the content of the compound contained in the coating layer can be appropriately adopted not only the above-mentioned method but also any conventionally known method. Even if an error occurs in the result depending on the measurement method, as long as the numerical value of the result measured by any one method is within a predetermined range, it can be considered that the requirement is satisfied even if the result measured by another measurement method is outside the predetermined range.

[0052] The halogen-based oxidizing agent-containing material having a coating layer of the present invention can be produced by forming a coating layer on a solid halogen-based oxidizing agent. The production method is not particularly limited, and known methods such as a stirring method, a rolling method, and a fluidized bed method may be employed, or a combination of these may be used. The halogen-based oxidizing agent-containing material can be produced by contacting the surface of the solid halogen-based oxidizing agent with a coating liquid containing a metal salt of a carboxylic acid or the like. For example, the halogen-based oxidizing agent-containing material can be produced according to or in accordance with the method described in Patent Document 3.

[0053] If the halogen-based oxidizing agent is a chlorine-based oxidizing agent, the available chlorine content (Cl ２The effective chlorine content of the chlorine-based oxidizing agent (Cl ２ As with the active chlorine content (converted value), it can be calculated by the above-mentioned formula 1 using iodometric titration. That is, the iodine liberated by the reaction of active chlorine with potassium iodide is titrated with a sodium thiosulfate solution, and the available chlorine content is calculated by formula 1.

[0054] The halogen-based oxidizing agent-containing material having a coating layer is solid and can take the form of, for example, powder, granules, tablets, etc. Powder is preferred. The average particle size of the halogen-based oxidizing agent-containing material having a coating layer is usually 1 to 5000 μm, preferably 10 to 3000 μm, and more preferably 50 to 2000 μm. This average particle size can be measured in accordance with the measurement method for "average particle size of composition" described below.

[0055] (Oxygen-Based Oxidizing Agent) The oxygen-based oxidizing agent refers to an organic or inorganic peroxide, a hydrogen peroxide adduct, or hydrogen peroxide, and examples thereof include percarbonates, perborates, peroxysulfates, and organic peroxides containing perbenzoic acid. Examples of percarbonates include sodium carbonate hydrogen peroxide adduct (sometimes simply referred to as sodium percarbonate) in which hydrogen peroxide is added to sodium carbonate. Examples of perborates include sodium perborate. Examples of peroxysulfates include pentapotassium peroxysulfate-sulfate, potassium peroxodisulfate, and mixtures thereof. From the viewpoints of ease of availability and ease of handling, the oxygen-based oxidizing agent is preferably one or more selected from the group consisting of sodium percarbonate, sodium perborate, pentapotassium peroxysulfate-sulfate (for example, "Oxone" (registered trademark) as an oxidizing agent containing pentapotassium peroxysulfate-sulfate), and mixtures thereof. From the viewpoints of reactivity to organic substances and oxidizing power, an oxidizing agent containing pentapotassium peroxysulfate-sulfate is particularly preferred.

[0056] The oxygen-based oxidizing agent is a solid and can take the form of, for example, powder, granules, tablets, etc. Powder is preferred. These forms can be prepared by known methods. The average particle size of the oxygen-based oxidizing agent is usually 1 to 5,000 μm, preferably 10 to 3,000 μm, and more preferably 50 to 2,000 μm. This average particle size can be measured in accordance with the measurement method for "average particle size of composition" described below.

[0057] Available oxygen content in oxygen-based oxidizing agents (O ２ The available oxygen content (equivalent to the active oxygen content) can be calculated by iodometric titration. That is, the iodine liberated by the reaction of active oxygen with potassium iodide is titrated with a sodium thiosulfate solution, and the available oxygen content is calculated by the following equation 4. In order to accelerate the reaction between active oxygen and potassium iodide, a small amount of an aqueous solution of ammonium molybdate adjusted to 1% by mass may be added.

[0058] Available oxygen content (%)=a×f×0.08000 / b (Formula 4) a: 0.1 N sodium thiosulfate solution (ml) required for titration b: sample (g) f: factor of 0.1 N sodium thiosulfate solution Oxygen-based oxidizing agents are commercially available and can be easily obtained, for example, from LANXESS under the trade name Oxone (registered trademark).

[0059] The content of the oxygen-based oxidizing agent in the composition of the present invention is usually 5 to 95% by weight, preferably 8 to 90% by weight, more preferably 10 to 80% by weight, and particularly preferably 10 to 70% by weight.

[0060] (Oxygen-based oxidizing agent-containing material having a coating layer) The oxygen-based oxidizing agent-containing material has a structure in which the surface of a solid oxygen-based oxidizing agent is covered with a coating layer. That is, the surface of the oxygen-based oxidizing agent such as particles, granules, tablets, etc. is protected by a coating layer. The oxygen-based oxidizing agent used here can be one described above.

[0061] The compound used for the coating layer is not particularly limited as long as it is a compound that can coat the surface of the oxygen-based oxidizing agent and suppress interaction between the oxygen-based oxidizing agent and the halogen-based oxidizing agent and other components.

[0062] Compounds that can be used for the coating layer include those listed in the above-mentioned "halogen-based oxidizing agent-containing material having a coating layer." These compounds may be used alone or in combination of two or more compounds. In an embodiment where two or more compounds are used in combination, two or more compounds may be mixed to form a coating layer containing multiple compounds, or a coating layer may be formed with one compound and then a further coating layer may be formed with another compound to form a multilayer structure.

[0063] The phrase "the oxygen-based oxidizing agent is coated with a coating layer" refers to a state in which the oxygen-based oxidizing agent is completely or incompletely coated with a coating layer, as long as the effects of the present invention are not impaired. Specifically, this includes both a case in which the entire amount of the oxygen-based oxidizing agent is coated with a coating layer and a case in which only a portion of the oxygen-based oxidizing agent is coated. It also includes a case in which the surface of each oxygen-based oxidizing agent in the form of powder or the like is completely coated with a coating layer and a case in which the surface is only a portion of the coating layer.

[0064] Among compounds that can be used for the coating layer, metal salts of carboxylic acids are more preferred because they are easy to process into a coating layer, have excellent function of protecting oxygen-based oxidants as a coating layer, and are easy to obtain and handle. Examples of metal salts of carboxylic acids include metal salts of aromatic carboxylic acids, metal salts of acyclic dicarboxylic acids, metal salts of acyclic monocarboxylic acids, metal salts of other carboxylic acids, and mixtures thereof.

[0065] The content of the oxygen-based oxidizing agent-containing material having a coating layer in the composition of the present invention is usually 5 to 95% by weight, preferably 8 to 92% by weight, more preferably 10 to 80% by weight, and particularly preferably 10 to 70% by weight.

[0066] From the viewpoint of facilitating the formation of a coating layer on the surface of a solid oxygen-based oxidizing agent, the content of the metal salt of carboxylic acid contained in the coating layer in the oxygen-based oxidizing agent-containing material is preferably 30% by weight or more, more preferably 50% by weight or more, and even more preferably 70% by weight or more, when the total weight of the coating layer is taken as 100% by weight.

[0067] The coating layer may contain various compounds such as inorganic and organic substances, as long as the effects of the present invention are not impaired. Examples of inorganic substances include, but are not limited to, phosphates, sulfates, silicates, chlorides, iodides, bromides, etc. Examples of organic substances include, but are not limited to, polysaccharides, polymeric compounds, and salts of organic substances.

[0068] The proportion (wt%) of the coating layer in an oxygen-based oxidant-containing composition having a coating layer, when the total weight of the oxygen-based oxidant-containing composition is taken as 100 wt%, is preferably 5 wt% or more, more preferably 10 wt% or more, and even more preferably 15 wt% or more, as a lower limit from the viewpoint of effectively suppressing the interaction between the oxygen-based oxidant and other components by the coating layer. Also, from the viewpoint of exerting the above-mentioned effect without an excessive proportion of the coating layer, the upper limit is preferably 70 wt% or less, more preferably 50 wt% or less, and even more preferably 45 wt% or less.

[0069] The proportion (wt%) of the oxygen-based oxidizing agent in the oxygen-based oxidizing agent-containing composition, when the total weight of the oxygen-based oxidizing agent-containing composition is taken as 100 wt%, is preferably 30 wt% or more as the lower limit, more preferably 50 wt% or more, and even more preferably 55 wt% or more, and is preferably 95 wt% or less as the upper limit, more preferably 90 wt% or less, and even more preferably 85 wt% or less.

[0070] In order to calculate the proportion of the coating layer in the oxygen-based oxidizing agent-containing material having the coating layer, the calculation method according to the following Equation 5 can be used.

[0071] Ratio of coating layer (wt %)=Q1×100 / Q2 (Formula 5) Q1: weight (g) of the coating layer in the oxygen-based oxidizing agent-containing material having the coating layer Q2: weight (g) of the oxygen-based oxidizing agent-containing material having the coating layer

[0072] The proportion of the coating layer can be calculated from the available oxygen content of the oxygen-based oxidizing agent-containing material using the following formula 6. In this case, if the oxygen-based oxidizing agent-containing material having a coating layer contains components other than the coating layer, such as moisture, the proportion of the coating layer can be obtained by subtracting the moisture content (or the content of components other than the coating layer) (wt %) from the calculation result.

[0073] Ratio of coating layer (wt%)=(P1-P2)×100 / P1 (Formula 6) P1: Available oxygen content (%) of the oxygen-based oxidizing agent used as raw material P2: Available oxygen content (%) of the oxygen-based oxidizing agent-containing material having a coating layer

[0074] The method for quantifying the proportion of the coating layer in the oxygen-based oxidant-containing material having a coating layer and the content of the compound contained in the coating layer can be any of the above-mentioned methods as well as any other conventionally known method. Even if an error occurs in the result depending on the measurement method, as long as the numerical value of the result measured by any one method is within a predetermined range, the requirement can be considered to be met even if the result measured by another measurement method is outside the predetermined range.

[0075] The oxygen-based oxidizing agent-containing material having a coating layer of the present invention can be produced by forming a coating layer on a solid oxygen-based oxidizing agent. The production method is not particularly limited, and known methods such as a stirring method, a rolling method, and a fluidized bed method may be employed, or a combination of these may be used. The oxygen-based oxidizing agent-containing material can be produced by contacting the surface of the solid oxygen-based oxidizing agent with a coating liquid containing a metal salt of a carboxylic acid or the like. For example, the oxygen-based oxidizing agent-containing material can be produced according to or in accordance with the method described in Patent Document 3.

[0076] Available oxygen content in oxygen-based oxidizing agent-containing material (O ２ The effective oxygen content of the oxygen-based oxidizer (O ２The available oxygen content can be calculated by iodometric titration, similarly to the equivalent value. That is, the iodine liberated by the reaction of active oxygen with potassium iodide is titrated with a sodium thiosulfate solution, and the available oxygen content is calculated by the above-mentioned formula 4. In order to accelerate the reaction between active oxygen and potassium iodide, a small amount of an aqueous solution of ammonium molybdate adjusted to 1% by mass may be added.

[0077] The oxygen-based oxidizing agent-containing material having a coating layer is solid and can take the form of, for example, powder, granules, tablets, etc. Powder is preferred. The average particle size of the oxygen-based oxidizing agent-containing material having a coating layer is usually 1 to 5000 μm, preferably 10 to 3000 μm, and more preferably 20 to 2000 μm. This average particle size can be measured in accordance with the measurement method for "average particle size of composition" described below.

[0078] The oxidizer content of a composition containing a mixture of chlorine-based oxidizer-containing and oxygen-based oxidizer-containing materials can be defined as the total oxidizer content. As described in Equation 1 and Equation 4, the available chlorine content (or available oxygen content) is calculated by titrating the iodine liberated by the reaction of active chlorine (or active oxygen) with potassium iodide using aqueous sodium thiosulfate solution. In the case of a composition containing a mixture of chlorine-based oxidizers and oxygen-based oxidizers, the sum of the iodine liberated by the chlorine-based oxidizer and the iodine liberated by the oxygen-based oxidizer is titrated using aqueous sodium thiosulfate solution. In this case, assuming that all of the liberated iodine is liberated by the chlorine-based oxidizer, the value calculated as the available chlorine content using Equation 1 is defined as the total oxidizer content. A decrease in both the available chlorine content and the available oxygen content, or either one of them, can be detected as a decrease in the total oxidizer content.

[0079] (Other Additives) The composition of the present invention can contain a combination of various compounds useful for water treatment. The composition of the present invention can contain other additives such as flocculants, organic acids, surfactants, chelating agents (metal ion traps), organic polymers, fragrances, dyes, enzymes, and inorganic substances, as long as the effects of the present invention are not impaired. Not only solid additives but also liquid additives can be used. For example, a liquid additive may be mixed in advance with a porous inorganic powder such as zeolite, etc., to support the liquid component on the inorganic substance, and then added.

[0080] The flocculant may contain one or more selected from the group consisting of inorganic flocculants, organic flocculants, and mixtures thereof. Although flocculants are sometimes called coagulants, in this specification, flocculants and coagulants are not distinguished as they are both compounds with the same effect.

[0081] Examples of inorganic flocculants include one or more selected from the group consisting of aluminum sulfate, aluminum hydroxide, aluminum chloride, polyaluminum chloride (sometimes referred to as PAC), aluminum sulfate (aluminum sulfate or aluminum potassium sulfate), aluminum oxide, ferric chloride, polyferric sulfate, ferrous sulfate, polysilica iron, hydrated lime (including calcium hydroxide), and mixtures thereof.

[0082] Examples of organic flocculants include one or more polymer flocculants selected from the group consisting of anionic polymer flocculants, nonionic polymer flocculants, cationic polymer flocculants, amphoteric polymer flocculants, and mixtures thereof. Examples of anionic polymer flocculants include copolymers of acrylamide and sodium acrylate, copolymers of acrylamide, sodium acrylate, and sodium 2-acrylamido-2-methylpropanesulfonate, and alkali metal salts of carboxymethylcellulose. Examples of nonionic polymer flocculants include polyacrylamide, alginic acid and its alkali metal salts, pectin, carboxymethylcellulose, polyacrylic acid and its alkali metal salts, polymaleic acid and its alkali metal salts, and acrylic acid-maleic acid copolymers and its alkali metal salts. Examples of cationic polymer flocculants include quaternary salts of polyalkylaminoalkyl methacrylate, copolymers of acrylamide and acrylic acid / acrylic acid / alkylaminoalkyl (meth)acrylate quaternary salts, homopolymers of cationic monomers such as dimethylaminoethyl acrylate or its quaternary salts, and dimethylaminoethyl methacrylate or its quaternary salts, or copolymers with acrylamide, polyvinylamidine, poly(diallyldimethylammonium chloride) (PDADMAC), polyethyleneimine, polyallylamine, polyvinylamine, poly(2-vinyl-1-methylpyridinium), dialkylamine-epichlorohydrin polycondensates, polylysine, polyamidine hydrochloride, chitosan, and diethylaminoethyl dextran. Examples of amphoteric polymer flocculants include copolymers of a cationic monomer such as dimethylaminoethyl acrylate or its quaternary salt or dimethylaminoethyl methacrylate or its quaternary salt, a nonionic monomer such as acrylamide, and acrylic acid or its salt, diallyldimethylammonium-acrylic acid copolymer, diallylmethylamine-maleic acid copolymer, etc. The ionicity of the polymer of the polymer flocculant may vary depending on the degree of polymerization or modification.

[0083] Among organic flocculants, cationic polymer flocculants having a quaternary ammonium salt are preferred from the viewpoint of neutralizing the surface charge of particles suspended in water to flocculate the particles. For example, diallyldimethylammonium polymers, diallyldimethylammonium-acrylic acid copolymers, diallylmethylamine-maleic acid copolymers, alkali metal salts thereof, halides thereof (particularly chlorides), and mixtures thereof are preferred, and poly(diallyldimethylammonium chloride) (PDADMAC), a type of diallyldimethylammonium polymer, is more preferred. These can be used as polymer flocculants. The weight average molecular weight of the polymer flocculant is not particularly limited, but the weight average molecular weight is preferably 1,000 to 50,000,000, and more preferably 2,000 to 30,000,000.

[0084] When a flocculant is contained in the composition, from the viewpoint of obtaining a sufficient flocculating effect, the content thereof is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, and even more preferably 0.3% by weight or more, when the weight of the entire composition is taken as 100% by weight. On the other hand, since further improvement of the flocculating effect cannot be expected even if an excessive amount is added, the content thereof is preferably 20% by weight or less, more preferably 15% by weight or less, and even more preferably 10% by weight or less.

[0085] The organic acid is not particularly limited, but is preferably one or more selected from oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, D-tartaric acid, L-tartaric acid, D-malic acid, L-malic acid, D-aspartic acid, L-aspartic acid, glutaric acid, D-glutamic acid, L-glutamic acid, citric acid, benzoic acid, and mixtures thereof, because they are solid and easy to handle at room temperature and normal pressure, and more preferably one or more selected from succinic acid, fumaric acid, and mixtures thereof, from the viewpoint of excellent blending stability with a solid halogen-based oxidizing agent (hypochlorous acid generating source) such as sodium dichloroisocyanurate.

[0086] The surfactant may be one or more selected from the group consisting of anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, and mixtures thereof.

[0087] Examples of the anionic surfactant include one or more selected from the group consisting of alkyl sulfate salts such as ammonium lauryl sulfate; alkylbenzene sulfonates such as sodium C12 to C14 branched or linear alkylbenzene sulfonate; sulfonates such as sodium C14 to C18 α-olefin sulfonate; dialkyl sulfosuccinates such as sodium dialkyl sulfosuccinate; alkyl phosphates such as potassium alkyl phosphate; polyoxyethylene alkyl ether sulfate salts such as sodium polyoxyethylene lauryl ether sulfate; alkyl sulfosuccinates such as sodium alkyl sulfosuccinate; and mixtures thereof.

[0088] Examples of nonionic surfactants include one or more selected from the group consisting of alkyl ethers such as lauryl alcohol alkoxylates; polyoxyethylene alkyl ethers such as polyoxyethylene higher alcohol ethers; EO-PO block polymers such as polyoxyethylene-polyoxypropylene block polymers, reverse-type polyoxyethylene-polyoxypropylene block polymers, polyoxyethylene-polyoxypropylene condensates, polyoxyethylene-polyoxypropylene block polymers of ethylenediamine, and reverse-type polyoxyethylene-polyoxypropylene block polymers of ethylenediamine; sorbitan fatty acid esters such as sorbitan laurate; polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan stearate; polyethylene glycol fatty acid esters such as polyethylene glycol laurate; polyoxyethylene alkylamines such as ethylenediamine-polyoxyethylene-polyoxypropylene block polymers; alkyl alkanolamides of lauric acid monoethanolamide; glycerin fatty acid esters such as stearic acid; sucrose fatty acid esters; and mixtures thereof.

[0089] Examples of cationic surfactants include one or more selected from the group consisting of alkylamine salts such as stearylamine acetate; quaternary ammonium salts such as distearyldimethylammonium salts, diisotetradecyldimethylammonium salts, cetylpyridinium chloride, benzethonium chloride, benzalkonium chloride, and didecyldimethylammonium chloride; and mixtures thereof.

[0090] Examples of amphoteric surfactants include alkyl betaines such as lauryl betaine, stearyl betaine, and 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine; amine oxides such as lauryl dimethylamine oxide; and one or more selected from the group consisting of these.

[0091] The surfactant is preferably an anionic surfactant from the viewpoint of excellent blend stability with halogen-based oxidizing agents such as sodium dichloroisocyanurate and oxygen-based oxidizing agents, and more preferably at least one selected from the group consisting of linear alkylbenzenesulfonate, sodium α-olefinsulfonate, sodium alkylsulfate, and mixtures thereof.

[0092] When a surfactant is contained in the coating layer of the halogen-based oxidizing agent-containing material or oxygen-based oxidizing agent-containing material having the coating layer, the content of the surfactant in the composition, including the surfactant contained in the coating layer, is preferably 0.1 wt % or more, more preferably 1 wt % or more, and even more preferably 2 wt % or more, relative to the weight of the composition, from the viewpoint of obtaining a sufficient surfactant effect.

[0093] The content of the surfactant in the composition is preferably 20% by weight or less, more preferably 10% by weight or less, and even more preferably 8% by weight or less, based on the weight of the composition.

[0094] Examples of organic polymers include organic polymers other than the compounds listed above as organic flocculants. Examples include one or more selected from the group consisting of polysaccharides such as carrageenan, guar gum, locust bean gum, alkali metal salts of alginic acid, dextrin, xanthan gum, starch, and derivatives thereof; methyl cellulose, ethyl cellulose, hydroxypropyl cellulose, hydroxyethyl cellulose, other cellulose derivatives, and mixtures thereof. Alternatively, examples include one or more organic polymers selected from the group consisting of polyvinyl alcohol, polyethylene glycol, olefin-maleic anhydride copolymers and alkali metal salts thereof, acrylic acid-sulfonic acid copolymers and alkali metal salts thereof, and mixtures thereof. While these organic polymers are not primarily used as flocculants, they may be used as flocculants depending on the properties of the treated water. They may also be incorporated into water treatment agents for viscosity adjustment, hardness component dispersant (agents that prevent calcium and magnesium salts from precipitating), dirt re-adhesion prevention, flocculant auxiliary, and other functions. Furthermore, multiple organic polymers may be used in combination.

[0095] When the composition contains an organic polymer, the content of the organic polymer is preferably 0.01 to 10 wt %, more preferably 0.1 to 7 wt %, and even more preferably 0.5 to 5 wt %, based on the total weight of the composition.

[0096] Examples of chelating agents that can be used include aminocarboxylic acid derivatives such as nitrilotriacetic acid, ethylenediaminetetraacetic acid, β-alaninediacetic acid, aspartic acid diacetic acid, methylglycine diacetic acid, iminodisuccinic acid, glutamic acid diacetic acid, metal salts thereof, and hydrates thereof; hydroxyaminocarboxylic acids such as serine diacetic acid, hydroxyiminodisuccinic acid, hydroxyethylethylenediaminetriacetic acid, dihydroxyethylglycine, metal salts thereof, and hydrates thereof; phosphonocarboxylic acid derivatives such as tripolyphosphoric acid, 1-diphosphonic acid, α-methylphosphonosuccinic acid, 2-phosphonobutane-1,2-dicarboxylic acid, metal salts thereof, and hydrates thereof; and mixtures thereof. From the viewpoints of availability, ease of handling, and metal ion capture effect, preferred are one or more chelating agents selected from the group consisting of aminocarboxylic acid metal salts, hydrates of aminocarboxylic acid metal salts, hydroxyaminocarboxylic acid metal salts, hydrates of hydroxyaminocarboxylic acid metal salts, and mixtures thereof. As the metal salt of the chelating agent, sodium salts are preferred. Sodium nitrilotriacetate is more preferred as a chelating agent from the viewpoint of excellent stability with halogen-based oxidizing agents and oxygen-based oxidizing agents. When a chelating agent is contained in the composition, the content of the chelating agent in the composition is preferably 0.1 to 80 wt %, more preferably 1 to 60 wt %, and even more preferably 1 to 40 wt %, based on the weight of the composition, from the viewpoint of metal ion capturing effect.

[0097] In addition to the inorganic flocculants described above, examples of inorganic substances include sulfates, acetates, carbonates, alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal chlorides, aluminum sulfates, siloxanes, clay minerals, boron compounds, etc. Inorganic substances can be incorporated for purposes such as builders (bulking) of the composition, pH adjustment, viscosity adjustment, flowability improvement, stabilizers for preventing blistering, and additives as markers for concentration control. When an inorganic substance is contained in the composition, the content of the inorganic substance in the composition is preferably 0.1 to 60 wt %, more preferably 1 to 40 wt %, and even more preferably 1 to 20 wt %, based on the weight of the composition.

[0098] Examples of sulfates include alkali metal sulfates such as lithium sulfate, sodium sulfate, and potassium sulfate, and alkaline earth metal sulfates such as magnesium sulfate and calcium sulfate. Examples of acetates include alkali metal acetates such as sodium acetate and potassium acetate, and alkaline earth metal acetates such as magnesium acetate and calcium acetate. Examples of carbonates include sodium bicarbonate, potassium bicarbonate, sodium carbonate, sodium carbonate, and lithium carbonate. Examples of alkali metal hydroxides include sodium hydroxide, potassium hydroxide, and lithium hydroxide. Examples of alkaline earth metal hydroxides include calcium hydroxide, magnesium hydroxide, and barium hydroxide. Examples of alkali metal chlorides include lithium chloride, sodium chloride, and potassium chloride. Examples of clay minerals include hectorite. Examples of boron compounds include borax, boric acid, metaboric acid, and boron oxide. Examples of siloxanes include dimethylpolysiloxane. These inorganic substances may be contained in the composition alone or in combination of two or more.

[0099] (Preparation of Composition) The composition of the present invention is characterized in that it contains a halogen-based oxidizing agent and an oxygen-based oxidizing agent, and either or both of the halogen-based oxidizing agent and the oxygen-based oxidizing agent are covered with a coating layer. Examples of this composition include the above-mentioned embodiments (1) to (3).

[0100] In the composition (1) above, the content of the oxygen-based oxidizing agent in the composition is typically 5 to 95 wt %, preferably 8 to 90 wt %, more preferably 10 to 80 wt %, and particularly preferably 10 to 70 wt %. The content of the halogen-based oxidizing agent-containing material having a coating layer in the composition is typically 5 to 95 wt %, preferably 8 to 92 wt %, more preferably 10 to 80 wt %, and particularly preferably 10 to 70 wt %. The content of the halogen-based oxidizing agent in the halogen-based oxidizing agent-containing material is typically 30 to 95 wt %, preferably 40 to 85 wt %, more preferably 50 to 80 wt %, and particularly preferably 60 to 80 wt %. When the composition contains a flocculant, the content of the flocculant in the composition is typically 0.01 to 20 wt %, preferably 0.1 to 15 wt %, and more preferably 0.3 to 10 wt %.

[0101] In the composition (2) above, the content of the halogen-based oxidizing agent in the composition is typically 5 to 95 wt %, preferably 8 to 90 wt %, more preferably 10 to 80 wt %, and particularly preferably 10 to 70 wt %. The content of the oxygen-based oxidizing agent-containing material having a coating layer in the composition is typically 5 to 95 wt %, preferably 8 to 92 wt %, more preferably 10 to 80 wt %, and particularly preferably 10 to 70 wt %. The content of the oxygen-based oxidizing agent in the oxygen-based oxidizing agent-containing material is typically 30 to 95 wt %, preferably 40 to 85 wt %, more preferably 50 to 80 wt %, and particularly preferably 55 to 80 wt %. When the composition contains a flocculant, the content of the flocculant in the composition is typically 0.01 to 20 wt %, preferably 0.1 to 15 wt %, and more preferably 0.3 to 10 wt %.

[0102] In the composition (3) above, the content of the halogen-based oxidizing agent having a coating layer in the composition is typically 5 to 95 wt %, preferably 8 to 93 wt %, more preferably 10 to 80 wt %, and particularly preferably 10 to 70 wt %. The content of the halogen-based oxidizing agent in the halogen-based oxidizing agent-containing material is typically 30 to 95 wt %, preferably 40 to 85 wt %, more preferably 50 to 80 wt %, and particularly preferably 60 to 80 wt %. The content of the oxygen-based oxidizing agent-containing material having a coating layer in the composition is typically 5 to 95 wt %, preferably 8 to 92 wt %, more preferably 10 to 80 wt %, and particularly preferably 55 to 80 wt %. The content of the oxygen-based oxidizing agent in the oxygen-based oxidizing agent-containing material is typically 30 to 95 wt %, preferably 40 to 85 wt %, more preferably 50 to 80 wt %, and particularly preferably 55 to 80 wt %. When the composition contains a flocculant, the content of the flocculant in the composition is usually 0.01 to 20% by weight, preferably 0.1 to 15% by weight, and more preferably 0.3 to 10% by weight.

[0103] Of the above embodiments (1) to (3), the composition (1) or (3) is preferred, and the composition (1) is more preferred.

[0104] The composition of the present invention is solid and can take the form of, for example, powder, granules, tablets, etc. Powder is preferred. The average particle size of the composition is usually 1 to 5000 μm, preferably 10 to 3000 μm, and more preferably 20 to 2000 μm. This average particle size can be measured as follows.

[0105] Using 13 sieves and a tray with openings of 75 μm, 106 μm, 150 μm, 250 μm, 425 μm, 600 μm, 710 μm, 850 μm, 1000 μm, 1180 μm, 1400 μm, 1700 μm, and 2000 μm, stack the sieves on top of the tray with the larger openings on top. The sample is placed on top of the 2000 μm sieve, and while supporting the stacked sieves with one hand, the sieve frame is tapped at a rate of approximately 120 times per minute. Occasionally, the sieves are placed horizontally and the sieve frame is tapped firmly several times. This procedure is repeated until the sieving is complete. If the sample is clumped together due to static electricity or if fine powder adheres to the inside or back of the sieve, gently loosen the sample with a brush and repeat the sieving process. The particles that pass through the sieve are considered to be undersized. Note that "undersized" refers to the test sample that passes through the sieve by the end of the sieving process. If the sample contains particles with a diameter exceeding 2000 μm, additional sieves with openings of 2360 μm, 2800 μm, 3350 μm, 4000 μm, 4750 μm, 5600 μm, or larger may be added. If there are many particles with a diameter of 75 μm or less, additional sieves with openings of 63 μm, 53 μm, 45 μm, 38 μm, or smaller may be added.

[0106] The mass of the particles remaining on each sieve and on the tray is measured, and the mass proportion (%) of the particles on each sieve is calculated. The mass proportions of the particles on the sieves with smaller openings are added together, starting from the tray, to calculate the average particle size. The opening of the first sieve whose accumulated mass proportion is 50% or more is defined as a μm, the opening of the sieve one size larger than a μm is defined as b μm, the accumulated mass proportion from the tray to the a μm sieve is defined as c%, and the mass proportion on the a μm sieve is defined as d%, and the average particle size can be calculated using the following formula 7.

[0107] Average particle diameter (μm) = 10 Ｓ (Equation 7)

[0108] The composition of the present invention can be produced by mixing a halogen-based oxidizing agent and an oxygen-based oxidizing agent, wherein either or both of the halogen-based oxidizing agent and the oxygen-based oxidizing agent have a coating layer. Other additives may be further added during mixing. Specifically, the composition (1) above can be prepared by mixing a halogen-based oxidizing agent and a halogen-based oxidizing agent-containing material having a coating layer covering its surface, and an oxygen-based oxidizing agent. The composition (2) above can be prepared by mixing an oxygen-based oxidizing agent and an oxygen-based oxidizing agent-containing material having a coating layer covering its surface, and a halogen-based oxidizing agent. The composition (3) above can be prepared by mixing a halogen-based oxidizing agent and a halogen-based oxidizing agent-containing material having a coating layer covering its surface, and an oxygen-based oxidizing agent and an oxygen-based oxidizing agent-containing material having a coating layer covering its surface.

[0109] Specifically, the mixing method involves adding the components to be contained in the composition to a known mixer and mixing them to obtain a mixture (composition). The resulting composition can be packaged in small containers such as films, pouches, or bottles. The container is not particularly limited as long as it can safely and stably store the composition, and examples of containers that can be used include aluminum laminate films, aluminum pouches, and resin bottles.

[0110] (Uses and Methods of Use of Composition) The composition of the present invention has excellent cleaning and bleaching abilities, and can be used for a variety of purposes. The composition of the present invention can be used for cleaning, sterilizing, purifying, etc. a wide range of water bodies, such as water in swimming pools, spas, fountains, hot tubs, cooling towers, and other water circulation facilities for landscaping or industrial use. Specifically, the target water body can be purified by treating the water body with the composition of the present invention. More specifically, the composition can be used as a pool shock agent, a water clarifier (transparency improver), or an organic matter reducer.

[0111] The composition of the present invention can be safely stored and used because heat generation caused by the interaction between the halogen-based oxidizing agent and the oxygen-based oxidizing agent when the composition comes into contact with a small amount of water is reduced. Furthermore, when the composition of the present invention is stored in a packaged state, the interaction between the halogen-based oxidizing agent and the oxygen-based oxidizing agent is reduced, thereby preventing swelling and damage to the package container. Therefore, deterioration of the active ingredient is suppressed, allowing for safe storage for a long period of time, making the composition easy to handle.

[0112] In order to effectively exert the effects of the composition of the present invention, particularly when treating pool water, the concentration of the composition in the aqueous solution after being added to the water body is preferably 0.1 to 1000 mg / L, more preferably 0.1 to 500 mg / L, and even more preferably 0.5 to 100 mg / L. The higher the concentration of the composition, the easier it is to obtain an effect, but adding an excessive amount does not provide further improvement in effect, and if the oxidizing agent concentration is too high due to the addition of an excessive amount of agent, it may increase the generation of nitrogen trichloride, which is irritating to mucous membranes such as the eyes, nose, and throat and may also cause an unpleasant odor, so it is preferable to avoid an agent concentration that is too high.

[0113] It is recommended that the concentration of the composition and the effective chlorine concentration be used within an appropriate range in accordance with the laws and guidelines of the country or region in which it is used. For example, in Japan, a notice from the Ministry of Health, Labor and Welfare (Notification No. 0528003, dated May 28, 2007) states that the hygiene standard for swimming pools is that the free residual chlorine (hereinafter sometimes referred to as free chlorine) concentration during swimming should be 0.4 mg / L or more, and preferably 1.0 mg / L or less. Therefore, when treating pool water with this composition, if there is a possibility that the free chlorine concentration will exceed the free chlorine concentration recommended by the hygiene standard, it is preferable to treat it at night when there are no swimmers or on days when the pool is closed. Even when using this composition in countries or regions other than Japan, it is recommended that it be used in accordance with the laws and guidelines of each country or region. In addition, the concentration used and the treatment time can be adjusted appropriately depending on the purpose, water quality, temperature used, and the desired degree of treatment of the water to be treated.

[0114] The effects of the present composition are explained based on the following hypothetical principle, but are not limited to this principle. For example, the application of the present composition to a body of water such as a swimming pool will be described. Generally, organic matter accumulates in pool water as the number of swimmers increases. This organic matter includes proteins and various compounds contained in sweat, sebum, and, in some cases, blood and urine. When chlorine-based oxidizing agents (hereinafter also referred to as chlorine agents) are added to water, they produce active chlorine such as hypochlorous acid (free chlorine: free hypochlorous acid molecules), which contributes to sterilization. When the number of swimmers increases and the concentration of these organic matter increases, not only can this cause cloudiness and odor in pool water, but the free chlorine added to sterilize the pool water can react with these organic matter and become inactive, or it can combine with nitrogen-containing organic matter such as proteins or nitrogen sources such as ammonia to form combined chlorine (chloramines: molecules composed of a nitrogen atom and a chlorine atom). Because combined chlorine has lower bactericidal properties than free chlorine, the conversion of free chlorine to combined chlorine is undesirable. Furthermore, nitrogen trichloride, a type of chloramine, is easily vaporized and has a pungent odor and is irritating to mucous membranes, which can cause deterioration of the swimming environment in indoor pools, etc., and therefore the generation of nitrogen trichloride is particularly undesirable.

[0115] One effective solution to this problem is to perform a water change on pool water with high organic matter concentrations. However, because water changes are costly and inconvenient, chemical treatments are sometimes used to reduce the organic matter concentration in pool water. One such chemical treatment is high-concentration chlorination (also known as shock treatment). By increasing the concentration of chlorine in the water, hypochlorous acid reacts with nitrogen-containing organic matter and other nitrogen sources, decomposing chloramines into nitrogen, thereby reducing the amount of nitrogen and combined chlorine in the water. This treatment decomposes the organic matter in the water, partially oxidizing it to nitrogen and carbon dioxide, which are then vaporized and released from the system, potentially reducing the organic matter concentration (potassium permanganate consumption). However, adding too much chlorine can increase the likelihood of by-products such as nitrogen trichloride being produced, so care should be taken not to use too high a chlorine concentration. Therefore, a composition such as this product, i.e., a mixture of chlorine agent and oxygen-based oxidizer (peroxysulfuric acid, sulfuric acid, and pentapotassium salt), can temporarily increase the concentration of chlorine agent due to the chlorine agent in the composition. In addition, peroxysulfuric acid, sulfuric acid, and pentapotassium salt can re-oxidize deactivated chloride ions in water, returning them to active chlorine. This means that the active chlorine concentration can be maintained without significantly increasing the amount of chlorine agent added, thereby reducing the risk of side effects such as the generation of nitrogen trichloride caused by excessive addition of chlorine agent.

[0116] The purpose of using this composition is to reduce the concentration of nitrogen sources and organic matter derived from organic matter and ammonia in pool water, and expected effects include a reduction in the concentration of organic matter in pool water (reducing potassium permanganate consumption), clarification (improving transparency), and suppression of the generation of undesirable by-products such as nitrogen trichloride.In addition, by maintaining the chlorine concentration in pool water, it is expected to reduce the occurrence of microbial contamination such as biofilm formation on the circulation path and the surfaces of the pool's inner walls, and to suppress the growth of algae in dormant pools.

[0117] When the composition of the present invention is used for, for example, pool water treatment, it is preferable to add the chemicals while a circulation system such as a filter is running in order to quickly dissolve the chemicals. The chemicals may be added directly to the pool tank, or, if a disinfectant-adding tank or disinfectant-adding device is installed in the circulation path, they may be added from there. However, since the addition of the chemicals temporarily increases the available chlorine concentration in the pool water, it is desirable to use the composition when the pool is not in use (no swimmers). When adding the composition, the composition of the present invention exerts a treatment effect (purification effect) on the water area. Therefore, particularly when treating pool water, the free chlorine concentration of the pool water is preferably 0.01 mg / L or more, more preferably 0.05 mg / L or more, even more preferably 0.1 mg / L or more, and most preferably 0.2 mg / L or more. On the other hand, from the viewpoint of preventing the effects of active chlorine on materials and piping, and of avoiding the generation of nitrogen trichloride as described above, the free chlorine concentration of the aqueous solution after adding the composition to the water is preferably 20 mg / L or less, more preferably 15 mg / L or less, even more preferably 10 mg / L or less, and most preferably 8 mg / L or less. The concentration can be adjusted appropriately depending on the swimming load of the pool water and whether it is an outdoor or indoor pool. The frequency of use of the composition may be about once a week, separately from the usual continuous chlorine management, or may be added before the pool is closed, or may be added immediately before swimming resumes after a period of closure. If the chlorine concentration is maintained within a range that does not affect swimmers, the composition may be used in parallel with the usual continuous chlorine management.

[0118] The composition of the present invention can be used for water treatment in spas and bathing facilities for the same purposes as in swimming pools, and can also be used to improve the water quality of landscape water (fountains, ornamental ponds, etc.) Patent Document 2 (U.S. Patent Publication No. 2006 / 0078584) is incorporated by reference.

[0119] The composition of the present invention can also be used in pulp treatment (particularly pulp bleaching). Conventionally, chlorine-based oxidizing agents or oxygen-based oxidizing agents have been used as bleaching agents for pulp bleaching. While the use of chlorine-based oxidizing agents in pulp bleaching has the excellent effect of efficiently decomposing residual lignin in pulp, in consideration of the environmental impact of organic chlorine compounds that may be generated as by-products when bleaching pulp with chlorine-based oxidizing agents, an ECF (elementary chlorine-free) bleaching method that uses as few chlorine-based compounds as possible is sometimes desired. Specifically, mechanical pulp, kraft pulp, and waste paper pulp produced through mechanical or chemical pulping treatment from wood or waste paper have a dark brown to cream color depending on the type of wood and the disintegration process. Bleaching these pulps requires a bleaching agent that decomposes the lignin contained in the pulp, but by treating the pulp with the composition of the present invention, both a chlorine-based oxidizing agent and an oxygen-based oxidizing agent act on the pulp while reducing the amount of chlorine-based oxidizing agent used, thereby producing bleached white pulp. Furthermore, as described above, the exemplary composition of the present invention, i.e., a mixture of a chlorine-based oxidizing agent and an oxygen-based oxidizing agent (peroxysulfuric acid, sulfuric acid, and pentapotassium salt), can temporarily increase the active chlorine concentration in water by the chlorine-based oxidizing agent in the composition, and the peroxysulfuric acid, sulfuric acid, and pentapotassium salt can reoxidize deactivated chloride ions in water to return them to active chlorine. Therefore, the active chlorine concentration can be maintained without significantly increasing the amount of chlorine-based oxidizing agent added, thereby reducing the risk of adverse environmental impacts caused by excessive addition of chlorine-based oxidizing agents.

[0120] Moreover, the brightness of pulp materials decreases over time. Treatment of bleached pulp materials with reduced brightness with the composition of the present invention can improve their brightness. Specifically, a pulp material with a desired improved brightness can be obtained by treating (contacting) a pulp material, such as pulp or bleached pulp, with a solution (aqueous solution) containing the composition of the present invention. For example, the composition of the present invention is added to an aqueous solution containing a pulp concentration adjusted to approximately 3 to 15% by mass at a temperature of 30 to 80°C and an alkaline (pH 8 to 11) or acidic (pH 3 to 6) pH level to a concentration of 0.1 to 30% by mass. The pulp is then contacted with the composition of the present invention and the reaction time is approximately 1 to 3 hours, resulting in a pulp material with improved brightness. Furthermore, additives such as oxidizing agents, reducing agents, chelating agents, and fluorescent brighteners can also be added to the solution containing the composition of the present invention depending on the intended purpose. In addition to the composition of the present invention, the method may further include a step of contacting the pulp with a chlorine-based oxidizing agent or an oxygen-based oxidizing agent alone, a step of contacting the pulp with a reducing bleaching agent such as hydrosulfite, a step of contacting the pulp with ozone or chlorine dioxide, or a post-treatment step of neutralization or washing. Kraft pulp, mechanical pulp, recycled paper pulp, etc. can be used as the pulp.

[0121] The present invention will be described in detail below using examples and comparative examples, but the present invention is not limited to these. The raw materials and experimental equipment used in the examples and comparative examples are as follows. [Raw Materials] Sodium dichloroisocyanurate: Shikoku Chemicals Corporation, product name "Neochlor 60MG (halogen-based oxidizing agent, hereinafter sometimes referred to as "SDIC")" (actual available chlorine content 62.7%, average particle size 339 μm) Sodium benzoate (coating layer component): reagent (Fujifilm Wako Pure Chemical Industries, Ltd.) Decanoic acid: reagent (Fujifilm Wako Pure Chemical Industries, Ltd.) Sodium hydroxide: reagent (Fujifilm Wako Pure Chemical Industries, Ltd.) Sodium decanoate aqueous solution: Decanoic acid was dispersed in distilled water, an equivalent amount of sodium hydroxide was added, and the mixture was stirred to obtain a sodium decanoate aqueous solution (sodium decanoate concentration 20 wt %). Heptanoic acid: Reagent (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) Sodium heptanoate aqueous solution: Heptanoic acid was dispersed in distilled water, and an equivalent amount of sodium hydroxide was added and stirred to obtain a sodium heptanoate aqueous solution (20% by weight sodium heptanoate concentration). Oxone (oxygen-based oxidant containing peroxysulfuric acid, sulfuric acid, and pentapotassium salt. Hereinafter, sometimes referred to as "OX" or "OXONE (registered trademark)" or "Oxone (registered trademark)"): Lanxess, trade name "OXONE (registered trademark)" (actual available oxygen content 4.81%, average particle size 386 μm) Poly(diallyldimethylammonium chloride) (polymer flocculant. Hereinafter, sometimes referred to as "PDADMAC")

[0122] [Aluminum laminate film] (for 30g storage stability test) Material composition (μm) [Outer layer] PET12 / AL7 / CPP50 [Aluminum laminate pouch bag] (for 460g storage stability test) Material composition (μm): [Outer layer] Polyester / AL / PE80 [Tumbling granulator] AS ONE "DPZ-1" [pH meter] HORIBA "F-51" [pH electrode] HORIBA "9615S-10D"

[0123] (Measurement of total oxidizer content and calculation of retention rate) The total oxidizer content (Cl) of each composition in the examples and comparative examples was ２The total oxidizer content (effective chlorine content) (%) was calculated using the above-mentioned iodometric titration method according to the following formula. Note that the following formula is substantially the same as Formula 1. Total oxidizer content (available chlorine content) (%) = a × f × 0.35452 / b a: 0.1 N sodium thiosulfate aqueous solution required for titration (ml) b: sample (g) f: factor of 0.1 N sodium thiosulfate aqueous solution The retention rate of the total oxidizer content was calculated by dividing the total oxidizer content of the composition after a certain period of time by the total oxidizer content of the composition before the start of the test, assuming that the total oxidizer content of the composition before the start of the test was 100%.

[0124] (Ratio of Coating Layer) The ratio of the coating layer used in the examples was calculated using Equation 3 in the case of a substance containing a chlorine-based oxidizing agent, and Equation 6 in the case of a substance containing an oxygen-based oxidizing agent.

[0125] (pH Measurement) Each composition of the Examples and Comparative Examples was dissolved in distilled water to a concentration of 1% by weight, and the solution was adjusted to 25°C. After stirring, approximately 50 ml of the aqueous solution was used to measure the pH with a pH meter. The pH meter was calibrated immediately before measurement using a pH 4 standard solution, a pH 7 standard solution, and a pH 9 standard solution.

[0126] (Measurement of Volume Change Rate) The volume change rate of the aluminum laminate film package or aluminum pouch package in which each composition of the Examples and Comparative Examples was sealed was evaluated. The volume change rate was calculated by dividing the volume of the aluminum laminate film package or aluminum pouch package after a certain period of time by the volume of the aluminum laminate film package or aluminum pouch package before the start of the test, assuming the volume of the aluminum laminate film package or aluminum pouch package before the start of the test to be 100%. The volume was measured by immersing the sealed aluminum laminate film package or aluminum pouch package in water measured in a measuring cylinder and reading the volume of the water surface that rose. The larger the volume change rate beyond 100%, the more severe the swelling of the aluminum laminate film package or aluminum pouch package.

[0127] Production Example 1 [Production of halogen-based oxidizing agent-containing material 1 having a coating layer (hereinafter sometimes referred to as "HOC1") and halogen-based oxidizing agent-containing material 1' having a coating layer (hereinafter sometimes referred to as "HOC1'")] Sodium benzoate, the compound used for the coating layer, was dissolved in water to a concentration of 30 wt % to prepare an aqueous coating solution. Powdered sodium dichloroisocyanurate was placed in a tumbling granulator ("DPZ-1" manufactured by AS ONE Corporation), and the tumbling granulator was rotated while heated to 60°C. The aqueous coating solution was sprayed onto the sodium dichloroisocyanurate flowing within the tumbling granulator. Spraying was stopped when a predetermined amount of coating layer was formed, yielding halogen-based oxidizing agent-containing material 1 (HOC1) having a coating layer. The available chlorine content of HOC1 was 43.7%, the coating layer ratio was 27.4 wt %, the water content was 2.90 wt %, and the average particle size was 855 μm. In addition, a halogen-based oxidizing agent-containing material 1' (HOC1') having a coating layer was prepared in the same manner as HOC1. The available chlorine content of HOC1' was 44.9%, the coating layer ratio was 25.5 wt%, the moisture content was 2.90 wt%, and the average particle size was 812 μm. HOC1 was used in Test Examples 1, 7, and 8, which will be described later, and HOC1' was used in Test Examples 5 and 6, which will be described later.

[0128] Production Example 2 [Production of Halogen-Based Oxidizing Agent-Containing Material 2 Having a Coating Layer (hereinafter, sometimes referred to as "HOC2")] Sodium decanoate was dissolved in water to a concentration of 20 wt % as the compound used for the coating layer to prepare an aqueous coating solution. Sodium decanoate was prepared by neutralizing decanoic acid with sodium hydroxide. A halogen-based oxidizing agent-containing material 2 (HOC2) having a coating layer was obtained in the same manner as in Production Example 1, except that an aqueous sodium decanoate solution was used as the coating solution. The available chlorine content of HOC2 was 45.9%, the proportion of the coating layer was 24.0%, and the water content was 2.8%. The average particle size was 1,474 μm.

[0129] Production Example 3 [Production of Oxygen-Based Oxidant-Containing Material 1 with a Coating Layer (hereinafter, sometimes referred to as "OC1")] Oxygen-based oxidant-containing material 1 with a coating layer (OC1) was obtained in the same manner as in Production Example 1, except that an oxygen-based oxidant (Oxone) containing peroxysulfuric acid, sulfuric acid, and pentapotassium salt was used instead of sodium dichloroisocyanurate. The available oxygen content of OOC1 was 3.67%, the coating layer ratio was 22.9 wt%, and the water content was 0.82 wt%. The average particle size was 692 μm.

[0130] Production Example 4 [Production of Oxygen-Based Oxidant-Containing Material 2 with a Coating Layer (hereinafter, sometimes referred to as "OOC2")] Sodium heptanoate, the compound used for the coating layer, was dissolved in water to a concentration of 20 wt % to prepare an aqueous coating solution. Sodium heptanoate was prepared by neutralizing heptanoic acid with sodium hydroxide. Oxygen-Based Oxidant-Containing Material 2 with a coating layer (OOC2) was obtained in the same manner as in Production Example 3, except that an aqueous sodium heptanoate solution was used for the coating solution. The available oxygen content of OOC2 was 3.14%, the coating layer ratio was 33.7 wt %, and the water content was 0.99 wt %. The average particle size was 1264 μm.

[0131] Test Example 1 [Temperature Change Test Due to Moisture Contamination] (1) Test Method Compositions (Comparative Examples 3 to 8) having the compositions shown in Table 1 were prepared by varying the ratio of powdered sodium dichloroisocyanurate (SDIC) and Oxone (registered trademark) (OX) as an oxygen-based oxidizing agent containing peroxysulfuric acid, sulfuric acid, and pentapotassium salt so that the total amount was 50 g. Also prepared were a powder of SDIC alone (Comparative Example 2), a powder of OX alone (Comparative Example 1), and a powder of halogen-based oxidizing agent-containing substance 1 (HOC1) with a coating layer alone (Comparative Example 9) (Table 1). The available chlorine content (ACL) (g) in Table 1 was calculated by multiplying the content (g) of the chlorine-based oxidizing agent or chlorine-based oxidizing agent-containing substance in the composition by the available chlorine content (%) of the chlorine-based oxidizing agent or chlorine-based oxidizing agent-containing substance calculated using Equation 1. Similarly, the values ​​of the available oxygen amount (AO) (g) in the table were calculated by multiplying the content (g) of the oxygen-based oxidizing agent or oxygen-based oxidizing agent-containing substance in the composition by the available oxygen content (%) of the oxygen-based oxidizing agent or oxygen-based oxidizing agent-containing substance calculated using Equation 4. The same applies to Tables 3, 5, 7, 9, and 11.

[0132] Each composition was placed in a 100 mL beaker, a glass thermometer graduated to 100°C was inserted into the center of the composition, and 5 mL of pure water was added around the thermometer to measure the temperature change over time near the point where the water was added.

[0133] Halogen-based oxidizer-containing material 1 (HOC1) with a coating layer was used instead of SDIC in the SDIC and OX compositions described above to prepare HOC1 and OX compositions (Examples 1-6) with the compositions listed in Table 1. The amounts of the SDIC contained in the compositions of Comparative Examples 3-8 and the HOC1 contained in the compositions of Examples 1-6 were adjusted so that their available chlorine contents (ACL) (g) were approximately equal. (The available chlorine content (%) of SDIC was 62.7%, and that of HOC1 was 43.7%. The same applies below.) The temperature change over time upon addition of water was measured for these samples in the same manner as described above. In all of the following temperature change tests due to water contamination, the ambient temperature during the test was 23-27°C, and the temperature of the pure water used before addition was 22-26°C. These conditions allowed for meaningful comparison of the temperature change measurement results for each composition.

[0134] (2) Results and Discussion The test results are shown in Table 2, Figures 1 and 2. As can be seen from Figure 1, when water was added to powder of SDIC alone (Comparative Example 2), heat was generated and the temperature rose to a maximum of 41°C (after 5 minutes). When water was added to powder of OX alone (Comparative Example 1), heat was absorbed and the temperature dropped to 16.5°C (after 1.5 minutes). When water was added to powder of HOC1 alone (Comparative Example 9), slight heat was generated and the temperature rose to 31°C (after 12 to 16 minutes).

[0135] In the case of the SDIC and OX compositions (Comparative Examples 3 to 8), the temperature rose rapidly within 5 minutes of adding water. In particular, the compositions of Comparative Example 4 (SDIC 20 g / OX 30 g), Comparative Example 5 (SDIC 22.7 g / OX 27.3 g), and Comparative Example 6 (SDIC 25 g / OX 25 g) generated significant heat, with Comparative Example 4 (SDIC 20 g / OX 30 g) reaching a maximum temperature of 93°C after 5 minutes.

[0136] In the case of the compositions of HOC1 and OX (Examples 1 to 6) according to the present invention, the temperature was measured up to 60 minutes after the addition of water (Table 2, Figure 2), but no significant exothermic peak was observed. The highest temperature was observed in Example 3 (HOC1 32.6 g / OX 27.3 g), where the temperature rose gradually to 43°C 20 minutes after the addition of water, but then gradually decreased. Therefore, it was found that when the amount of water added was 5 mL, the compositions of HOC1 and OX (Examples 1 to 6) were able to dramatically suppress heat generation compared to the compositions of SDIC and OX (Comparative Examples 3 to 8).

[0137]

[0138]

[0139] Test Example 2 [Temperature Change Test Due to Water Contamination] (1) Test Method: Compositions of HOC2 and OX (Examples 7 and 8) with the compositions listed in Table 3 were prepared in the same manner as in Test Example 1, except that a halogen-based oxidizing agent-containing material 2 (HOC2) with a coating layer was used. The amounts of the compositions of Examples 7 and 8 were adjusted so that the available chlorine content (ACL) (g) of the SDIC contained in the compositions of Comparative Examples 5 and 6 and the available chlorine content (ACL) (g) of the HOC2 contained in the compositions of Examples 7 and 8 were approximately equivalent. (The available chlorine content (%) of SDIC was 62.7%, and the available chlorine content (%) of HOC2 was 45.9%. The same applies below.) The temperature change over time upon addition of water to this sample was measured in the same manner as above. A test was also conducted on HOC2 alone as Comparative Example 10.

[0140] (2) Results and Discussion The test results are shown in Table 4 and Figure 3. When water was added to powder of SDIC alone (Comparative Example 2) and when water was added to powder of OX alone (Comparative Example 1), the results were the same as in Test Example 1, but when water was added to powder of HOC2 alone (Comparative Example 10), the temperature rose slightly to 26.5°C (after 12 to 20 minutes).

[0141] In the case of the SDIC and OX compositions (Comparative Examples 5 and 6), similar to Test Example 1, the compositions of Comparative Example 5 (SDIC 22.7 g / OX 27.3 g) and Comparative Example 6 (SDIC 25 g / OX 25 g) generated intense heat, reaching a maximum temperature of 90°C after 3 minutes. On the other hand, in the case of the HOC2 and OX compositions (Examples 7 and 8) of the present invention, the temperature was measured up to 60 minutes after the addition of water (Table 4, Figure 3), but no significant exothermic peak was observed. The highest temperature was observed in Example 8 (HOC2 34.2 g / OX 27.3 g), which gradually rose to 33°C 40 minutes after the addition of water, but then gradually decreased in temperature. Therefore, it was found that when the water input amount was 5 mL, the HOC2 and OX compositions (Examples 7 and 8) were able to dramatically suppress heat generation compared to the SDIC and OX compositions (Comparative Examples 5 and 6).

[0142]

[0143]

[0144] Test Example 3 [Temperature Change Test Due to Water Contamination] (1) Test Method: Similar to Test Example 1, compositions of SDIC and OOC1 (Examples 9-13) with the compositions listed in Table 5 were prepared using oxygen-based oxidant-containing material 1 (OC1) with a coating layer. The amounts of the compositions of Examples 9-13 were adjusted so that the available oxygen content (AO) (g) of the OOC1 contained in the compositions of Comparative Examples 4-8 was approximately equal to that of the OOC1 contained in the compositions of Examples 9-13. (The available oxygen content (%) of OX was 4.81%, and the available oxygen content (%) of OOC1 was 3.67%. The same applies below.) The temperature change over time upon addition of water to these samples was measured in the same manner as above. A test was also conducted on OOC1 alone as Comparative Example 11.

[0145] (2) Results and Discussion The test results are shown in Table 6 and Figure 4. When water was added to powder of SDIC alone (Comparative Example 2) and when water was added to powder of OX alone (Comparative Example 1), the results were the same as in Test Example 1, but when water was added to powder of OOC1 alone (Comparative Example 11), the temperature rose slightly to 32°C (after 12 to 20 minutes).

[0146] In the case of the SDIC and OX compositions (Comparative Examples 4 to 8), similar to Test Example 1, the compositions of Comparative Example 4 (SDIC 20 g / OX 30 g), Comparative Example 5 (SDIC 22.7 g / OX 27.3 g), and Comparative Example 6 (SDIC 25 g / OX 25 g) showed intense heat generation, reaching a maximum temperature of 90-93°C after 3 to 5 minutes. On the other hand, in the case of the SDIC and OOC1 compositions (Examples 9 to 13) according to the present invention, the temperature was measured for 60 minutes after the addition of water (Table 6, Figure 4). The highest temperature was observed in Example 10 (SDIC 22.7 g / OOC1 35.8 g), which rose slowly to 62.5°C 16 minutes after the addition of water, but then gradually decreased. Therefore, it was found that when the amount of water added was 5 mL, the compositions of SDIC and OOC1 (Examples 9 to 13) were able to suppress heat generation compared to the compositions of SDIC and OX (Comparative Examples 4 to 8).

[0147]

[0148]

[0149] Test Example 4 [Temperature Change Test Due to Water Contamination] (1) Test Method: Similar to Test Example 3, compositions of SDIC and OOC2 (Examples 14-17) with the compositions listed in Table 7 were prepared using oxygen-based oxidant-containing material 2 (OOC2) with a coating layer. The amounts of the OX contained in the compositions of Comparative Examples 4-7 and the OOC2 contained in the compositions of Examples 14-17 were adjusted so that the available oxygen amounts (AO) (g) of the OX and OOC2 were approximately equal. (The available oxygen content (%) of the OX was 4.81%, and the available oxygen content (%) of the OOC2 was 3.14%. The same applies below.) The temperature change over time upon addition of water to these samples was measured in the same manner as in Test Examples 1-3. A test was also conducted on OOC2 alone as Comparative Example 12.

[0150] (2) Results and Discussion The test results are shown in Table 8 and Figure 5. When water was added to powder containing SDIC alone (Comparative Example 2) and when water was added to powder containing OX alone (Comparative Example 1), the results were the same as in Test Example 1. However, when water was added to powder containing OOC2 alone (Comparative Example 12), the temperature rose slightly to 31°C (after 14 to 40 minutes).

[0151] In the case of the SDIC and OX compositions (Comparative Examples 4 to 7), similar to Test Example 1, the compositions of Comparative Example 4 (SDIC 20 g / OX 30 g), Comparative Example 5 (SDIC 22.7 g / OX 27.3 g), and Comparative Example 6 (SDIC 25 g / OX 25 g) generated intense heat, reaching a maximum temperature of 90-93°C after 3 to 5 minutes. On the other hand, in the case of the SDIC and OOC2 compositions (Examples 14 to 17) according to the present invention, the temperature was measured for 60 minutes after the addition of water (Table 8, Figure 5). The highest temperature was observed in Example 15 (SDIC 22.7 g / OOC2 41.8 g), which rose slowly to 51°C 10 minutes after the addition of water, but then gradually decreased. Therefore, it was found that when the amount of water added was 5 mL, the compositions of SDIC and OOC2 (Examples 14 to 17) were able to suppress heat generation compared to the compositions of SDIC and OX (Comparative Examples 4 to 7).

[0152]

[0153]

[0154] Test Example 5 [Temperature Change Test Due to Water Contamination] (1) Test Method Using HOC1' and OOC1, compositions of HOC1' and OOC1 (Examples 18-22) having the compositions set forth in Table 9 were prepared in the same manner as in Test Examples 1-4. The amounts of SDIC and OX contained in the compositions of Comparative Examples 4-7 and the available chlorine amount (ACL) (g) of HOC1' and the available oxygen amount (AO) (g) of OOC1 contained in the compositions of Examples 18-22 were adjusted so that they were approximately equivalent. The temperature change over time upon addition of water to these samples was also measured in the same manner as in Test Examples 1-4.

[0155] (2) Results and Discussion The test results are shown in Table 10 and Figure 6. When water was added to powder of SDIC alone (Comparative Example 2) and when water was added to powder of OX alone (Comparative Example 1), the results were the same as Test Example 1. When water was added to powder of HOC1 alone (Comparative Example 9) and when water was added to powder of OOC1 alone (Comparative Example 11), the results were the same as Test Examples 1 and 3, respectively.

[0156] In the case of the SDIC and OX compositions (Comparative Examples 4 to 7), similar to Test Example 1, the compositions of Comparative Example 4 (SDIC 20 g / OX 30 g), Comparative Example 5 (SDIC 22.7 g / OX 27.3 g), and Comparative Example 6 (SDIC 25 g / OX 25 g) generated intense heat, reaching a maximum temperature of 90 to 93°C after 3 to 5 minutes. On the other hand, in the case of the compositions of HOC1' and OOC1 (Examples 18 to 22), which are embodiments of the present invention, the temperature was measured up to 60 minutes after the addition of water (Table 10, Figure 6), but no noticeable exothermic peak was observed. The highest temperatures were observed in Example 19 (HOC1' 31.7g / OOC1 35.8g) and Example 20 (HOC1' 34.9g / OOC1 32.7g), where the temperature gradually rose to 33°C 20 minutes after adding water, but then gradually decreased. Therefore, when the amount of water added was 5mL, it was found that the compositions of HOC1' and OOC1 (Examples 18 to 22) were able to dramatically suppress heat generation compared to the compositions of SDIC and OX (Comparative Examples 4 to 7).

[0157]

[0158]

[0159] Test Example 6 [Temperature Change Test Due to Water Contamination] (1) Test Method: Compositions of HOC1' and OOC2 (Examples 23 to 25) having the compositions shown in Table 11 were prepared in the same manner as in Test Example 5, except that OOC2 was used instead of OOC1. The amounts of SDIC and OX contained in the compositions of Comparative Examples 4 to 6 were adjusted so that the available chlorine amount (ACL) (g) of HOC1' and the available oxygen amount (AO) (g) of OOC2 contained in the compositions of Examples 23 to 25 were approximately equivalent. The temperature change over time when water was added to these samples was measured in the same manner as in Test Example 5.

[0160] (2) Results and Discussion The test results are shown in Table 12 and Figure 7. When water was added to powder of SDIC alone (Comparative Example 2) and when water was added to powder of OX alone (Comparative Example 1), the results were the same as Test Example 1. When water was added to powder of HOC1 alone (Comparative Example 9) and when water was added to powder of OOC2 alone (Comparative Example 12), the results were the same as Test Examples 1 and 4, respectively.

[0161] In the case of the SDIC and OX compositions (Comparative Examples 4-6), similar to Test Example 1, the compositions of Comparative Example 4 (SDIC 20g / OX 30g), Comparative Example 5 (SDIC 22.7g / OX 27.3g), and Comparative Example 6 (SDIC 25g / OX 25g) generated intense heat, reaching a maximum temperature of 90-93°C after 3-5 minutes. In contrast, for the compositions of HOC1' and OOC2 (Examples 23-25) according to the present invention, the temperature was measured up to 60 minutes after the addition of water (Table 12, Figure 7). The highest temperature was observed in Example 24 (HOC1' 31.7g / OOC2 41.8g), which gradually rose to 38.5°C 18 minutes after the addition of water, followed by a gradual decrease in temperature. Therefore, it was found that when the amount of water input was 5 mL, the compositions of HOC1′ and OOC2 (Examples 23 to 25) could dramatically suppress heat generation compared to the compositions of SDIC and OX (Comparative Examples 4 to 6).

[0162]

[0163]

[0164] Test Example 7 [Storage Stability Test (Accelerated Test)] (1) Test Method <30 g / Packaged in Aluminum Laminate Film> 30 g of a composition containing SDIC and OX (Comparative Example 13) and 30 g of a composition containing HOC1 and OX (Example 26) having the compositions shown in Table 13 were prepared, each packaged in an aluminum laminate film sealed on three sides and formed into a bag, and then heat-sealed and stored under accelerated conditions (40°C / 75% RH and 50°C / 30% RH).

[0165] <460 g / Aluminum Pouch Packaging> 460 g of a composition containing SDIC and OX (Comparative Example 14) and 460 g of a composition containing HOC1 and OX (Example 27) having the compositions shown in Table 13 were prepared, packaged in aluminum pouches, heat-sealed, and stored under accelerated conditions (40°C / 75% RH and 50°C / 30% RH). In the accelerated tests, after 1, 1.5, 2, and 3 months at 40°C / 75% RH and after 1 and 2 months at 50°C / 30% RH, a portion of each composition was taken out and the available chlorine content (Cl ２The pH of the 1% aqueous solution, the volume change rate of the aluminum laminate film packaging or aluminum pouch packaging (presence or absence of swelling), and the appearance change of the aluminum pouch packaging were measured or confirmed (N=3 for each).

[0166]

[0167]

[0168]

[0169] (2) Results and Discussion: As shown in Table 14, in the test for 30 g / aluminum laminate film packaging, both Comparative Example 13 and Example 26 maintained a high retention rate of approximately 90% or more of the total oxidizer content compared to the initial value after three months of storage at 40°C / 75% RH and after two months of storage at 50°C / 30% RH. The pH (1% aqueous solution) of both Comparative Example 13 and Example 26 tended to decrease slightly from the initial value after three months of storage at 40°C / 75% RH and after two months of storage at 50°C / 30% RH, but no significant difference was observed between the Comparative Example and Example. On the other hand, when Comparative Example 13 and Example 26 were compared under the same conditions and storage periods, the volume increase (swelling) of the aluminum laminate film packaging of Example 26 was significantly smaller than that of Comparative Example 13 under both conditions of 40°C / 75% RH and 50°C / 30% RH.

[0170] From this, it is believed that in Comparative Example 13, OX and SDIC reacted in some way during the accelerated test, generating gas. On the other hand, in Example 26, in which HOC1 was used instead of SDIC, almost no swelling of the aluminum laminate film packaging occurred under any of the accelerated conditions. From this, it is believed that the use of HOC1 suppresses the reaction between OX, an oxygen-based oxidizing agent, and SDIC, a chlorine-based oxidizing agent, during storage, even under accelerated conditions.

[0171] As shown in Table 15, in the test for <460 g / aluminum pouch packaging>, for Comparative Example 14, aluminum corrosion was observed on the sides and bottom of the aluminum pouch packaging after one month of storage under storage conditions of 40°C / 75% RH (see Figure 8). Therefore, volume measurement was not possible. Furthermore, after 1.5 months of storage, corrosion of the aluminum pouch packaging had progressed further (see Figure 9), so the test was discontinued. For Example 27, no aluminum corrosion of the aluminum pouch packaging was observed even after three months of storage at 40°C / 75% RH, and the volume change rate was only 103%. For Comparative Example 14, aluminum corrosion was observed on the bottom of the aluminum pouch packaging after two months of storage at 50°C / 30% RH (see Figure 10). Therefore, volume measurement was not possible. For Example 27, no aluminum corrosion of the aluminum pouch packaging was observed even after two months of storage at 50°C / 30% RH, and the volume change rate was only 106%.

[0172] Test Example 8 [Aqueous Solution Stability Test] (1) Test Method 1.198 g of the composition of Comparative Example 13 and 1.427 g of the composition of Example 26 were each added to 1 L of distilled water at 25°C and dissolved to prepare aqueous solutions. Immediately after preparation, the aqueous solutions were left to stand at the same temperature, and after 1, 3, 5, 8, and 24 hours, aqueous solutions were sampled from the aqueous solutions using a 100 mL volumetric pipette, and the pH and available chlorine content of the aqueous solutions were measured and recorded. The results are shown in Table 16.

[0173] (2) Results and Discussion As shown in Table 16, there was no significant difference between Comparative Example 13 and Example 26 in terms of the retention rate of available chlorine content in aqueous solution and the transition of pH. This confirmed that the combination of HOC1 and OX exhibits the same effect as the combination of SDIC and OX in removing water turbidity and algae growth. In other words, even when a halogen-based oxidizing agent having a coating layer is used instead of a conventional chlorine-based oxidizing agent, it can be expected to exhibit effectiveness as an oxidizing agent.

[0174]

[0175] The present invention can provide a composition that has high water treatment and bleaching effects, suppresses heat generation when water is added to the composition, suppresses swelling and damage to packaging containers during storage, and has excellent storage stability, and has industrial applicability.

Claims

1. A solid composition containing a halogen-based oxidizing agent and an oxygen-based oxidizing agent, wherein either or both of the halogen-based oxidizing agent and the oxygen-based oxidizing agent are covered with a coating layer.

2. The composition according to claim 1, which is one composition selected from the group consisting of the following (1) to (3): (1) a composition containing a halogen-based oxidizing agent and a halogen-based oxidizing agent-containing material having a coating layer covering its surface, and an oxygen-based oxidizing agent; (2) a composition containing an oxygen-based oxidizing agent and an oxygen-based oxidizing agent-containing material having a coating layer covering its surface, and a halogen-based oxidizing agent; and (3) a composition containing a halogen-based oxidizing agent and a halogen-based oxidizing agent-containing material having a coating layer covering its surface, and an oxygen-based oxidizing agent and an oxygen-based oxidizing agent-containing material having a coating layer covering its surface.

3. The composition according to claim 1 or 2, wherein the coating layer comprises one or more selected from the group consisting of metal salts of carboxylic acids, surfactants, polysaccharides, higher fatty acids, paraffin wax, zeolites, and resins.

4. The composition of claim 3, wherein the coating layer comprises a metal salt of a carboxylic acid, and the metal salt of a carboxylic acid is one or more selected from the group consisting of an alkali metal salt of an aromatic carboxylic acid, an alkali metal salt of an acyclic dicarboxylic acid, an alkali metal salt of an acyclic monocarboxylic acid, and mixtures thereof.

5. The composition of claim 2, wherein said composition further comprises a flocculating agent.

6. The composition according to claim 2, which is the composition (1).

7. The composition according to claim 6, wherein the content of said halogen-based oxidizing agent in said composition is 5% by weight or more and 95% by weight or less.

8. The composition according to claim 6, wherein the content of the halogen-based oxidizing agent in the halogen-based oxidizing agent-containing material is 30% by weight or more and 95% by weight or less.

9. The composition according to claim 6, wherein the content of said oxygen-based oxidizing agent in said composition is 5% by weight or more and 95% by weight or less.

10. A method for producing the composition described in claim 6, comprising the step of mixing a halogen-based oxidizing agent and a halogen-based oxidizing agent-containing material having a coating layer covering the surface of the halogen-based oxidizing agent, and an oxygen-based oxidizing agent.

11. The method according to claim 10, comprising the step of contacting a coating liquid with a surface of a halogen-based oxidizing agent to produce a halogen-based oxidizing agent-containing material.

12. The composition according to claim 2, which is the composition (3).

13. A method for producing the composition described in claim 12, comprising the step of mixing a halogen-based oxidizer-containing substance having a halogen-based oxidizer and a coating layer covering its surface, and an oxygen-based oxidizer-containing substance having an oxygen-based oxidizer and a coating layer covering its surface.

14. A method for treating a body of water comprising the step of applying to said body of water a composition as defined in claim 1.

15. A method for treating pulp, comprising the step of contacting the pulp with the composition of claim 1.

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