Solid bleaching agent containing substance and cleaning agent composition

Abstract

The present invention relates to a solid bleaching agent content and a cleaning agent composition. There is a need for a stabilized solid bleaching agent that does not blister, has good solubility in water, and does not produce residues. The present invention provides a stabilized solid bleaching agent-containing substance in which a coating layer is formed, the coating layer contains at least one selected from the group consisting of an alkali metal salt of an aromatic carboxylic acid, an alkali metal salt of a non-cyclic dicarboxylic acid, an alkali metal salt of a non-cyclic monocarboxylic acid having 1-7 carbon atoms, and mixtures thereof.

Description

[0001] The present patent application is a divisional application of the Chinese Patent Application No. 201780024664.3, filed on April 21, 2017, entitled "Solid Bleach Containing Material and Detergent Composition". TECHNICAL FIELD

[0002] The present invention relates to a solid bleach containing material and a detergent composition, and more particularly to a solid bleach containing material and a detergent composition having a coating layer. BACKGROUND

[0003] In order to clean a drain pipe, a water storage portion of a kitchen, a bathroom, a washroom, a toilet, and the like; to wash laundry and the like; to clean tableware, cooking utensils; to keep bath water, pool water, and the like clean, a solid bleach is widely used for the purpose of cleaning, sterilization, bleaching, and the like. Such a solid bleach is used in various shapes such as a powder, a granule, a tablet, and the like according to the purpose, and is sometimes used in mixture with other ingredients such as various surfactants, alkali agents, metal ion capturing agents, and the like which contribute to cleaning.

[0004] Thus, in the case where the solid bleach is used in mixture with other ingredients, the solid bleach reacts with the other ingredients due to the high reactivity of the solid bleach. As a result, not only the deterioration, inactivation, decomposition of the solid bleach, but also the decomposition, deterioration of the other ingredients are caused at the same time, and thus the effects of cleaning, sterilization, bleaching, and the like are remarkably reduced. Therefore, in order to prevent the reaction of the solid bleach with the other ingredients, a method of coating or encapsulating the solid bleach has been proposed.

[0005] For example, in Patent Literature 1 and Patent Literature 2, the following gist is disclosed: by forming a first layer containing an inorganic salt and a second layer containing a synthetic surfactant such as a n-alkyl sulfonate on the surface of a chlorinated isocyanuric acid compound which is a core component of an active halogen-containing bleach agent, the stability of the chlorinated isocyanuric acid compound is improved. In addition, in Patent Literature 3, a bleach agent particle encapsulated with a fatty acid soap having 16 to 18 carbon atoms and an alkali metal fatty acid soap having 12 to 14 carbon atoms is disclosed. However, these synthetic surfactants, fatty acid soaps are surfactants having high foaming properties, and when the bleach agent particle containing such a surfactant is used, excessive rinsing work is required after use in order to flush the foam, and for example, in the case of recycling water used in a work tableware washing machine, a cooling device, and the like, a problem occurs in that the foam is sucked into the inside of a pump and the flow rate is reduced, and the like. In addition, in a tableware washing machine, in order to jet a cleaning liquid at high pressure, non-foaming properties are required. Therefore, for the bleach agent particle containing such a surfactant, there remains a problem that the use is limited in the case where foaming properties are not required, in the case where foaming properties hinder the use, and the like.

[0006] In Patent Literature 4, a particle in which a bleaching agent is enclosed with one or more paraffins having a melting point of 40 to 50°C and a solid content of 35 to 100% at 40°C and 0 to 15% at 50°C is disclosed. However, such paraffins are not soluble in water, and therefore in the case of use under conditions where the temperature does not satisfy the melting point, there is a problem that the bleaching agent cannot be substantially released into the cleaning water and the particle itself becomes a residue and remains. In addition, even in the case of use under conditions where the temperature is greater than 40°C, the melted paraffin is not soluble in water, and therefore an emulsifier or the like needs to be separately added in order to prevent the remaining of the paraffin. Furthermore, when the temperature decreases after use, there is a problem that it again becomes a residue or the like.

[0007] In Patent Literature 5, a bleaching agent coated with a plurality of layers including a saturated fatty acid, a microcrystalline wax, and a polyoxyethylene-polyoxypropylene copolymer is disclosed. In addition, in Patent Literature 6, a bleaching agent encapsulated particle is described, which includes a first coating agent containing a paraffin or the like and a second coating agent containing a powder of an A-type zeolite and calcium stearate. However, with such a coating, since the saturated fatty acid, the microcrystalline wax, the paraffin, the A-type zeolite, and the calcium stearate are not soluble in water, there is a problem of remaining residue as in the case of the invention described in Patent Literature 4. Furthermore, the organic polymer such as polyoxyethylene-polyoxypropylene has reactivity with the solid bleaching agent, and therefore it is necessary to provide a layer of a fatty acid or the like to isolate so that the solid bleaching agent does not directly contact the polyoxyethylene-polyoxypropylene, and there is a problem that the process becomes complicated. Moreover, in the case of using these organic polymers or the like for coating, it is extremely difficult to perform the process while completely preventing the organic polymer from contacting the solid bleaching agent from the start of the manufacturing to the end of the use, and there is a problem that the degradation, deactivation, decomposition of the bleaching agent, and the decomposition of other materials are likely to occur during the process.

[0008] In Patent Literature 7, a powder detergent for an automatic dishwashing machine is described, which includes a particulate oxidizing component having a poly(carboxylic acid ester) envelope such as a poly(methacrylic acid). However, such a poly(carboxylic acid ester) is not soluble in water at a usual neutral pH, and the solubility in water is slightly improved at an alkaline pH, but the problem of the generation of residue is not solved. In addition, the poly(carboxylic acid ester) has reactivity with an oxidizing halogen-containing bleaching agent due to a functional group such as an ester group within the molecule, and therefore in the case of coating a bleaching agent with a polymer containing such a functional group, the decomposition reaction slowly proceeds between the poly(carboxylic acid ester) and the bleaching agent, the coating deteriorates, and therefore adverse effects are brought to the storage stability, and there is a problem that the bleaching agent is degraded, deactivated, and decomposed due to the reaction with the coating agent.

[0009] A chlorine-containing bleaching agent composition containing a solid chlorine-containing bleaching agent and sodium benzoate in a tablet form is disclosed in Patent Literature 8. However, only the effect of reducing the hygroscopicity of the tablet and the lubricating effect by compounding sodium benzoate are suggested, whereby the tabletability is improved, but no other ingredients such as various surfactants, alkaline agents, metal ion capturing agents, and the like which contribute to cleaning are mixed with the solid chlorine-containing bleaching agent, and there is no suggestion that sodium benzoate can be used for a coating layer.

[0010] From these prior art documents, it is considered that a surfactant having a large molecular weight, a polysaccharide, a hydrocarbon such as wax, a high molecular polymer, and the like are suitable as a coating material used for stabilization of a solid bleaching agent. However, in the case where these compounds are used for a coating layer, the effect of protecting the solid bleaching agent is insufficient, and there are cases where these compounds themselves react with the solid bleaching agent. In addition, the solid bleaching agent is reactive with many organic substances, so it is necessary to select from a limited range of compounds, and the problems of foaming and residue generation are not solved.

[0011] On the other hand, in the case where a water-soluble inorganic salt or the like is used as a coating material, although it is possible to avoid the generation of undesirable foaming and residue, the water-soluble inorganic salt itself does not form a coating layer, so it is not suitable as a coating material, or even if a coating layer is formed, it has the disadvantage that the stabilizing effect (protection of the solid bleaching agent from factors such as deterioration, deactivation, decomposition, and the like) is low. In order to compensate for these disadvantages, it is necessary to use a water-soluble inorganic salt in combination with the surfactant having a large molecular weight, the polysaccharide, the hydrocarbon such as wax, the high molecular polymer, and the like to form a multilayer coating film or the like.

[0012] As described above, there is a demand for a solid bleaching agent containing agent having a coating layer which does not foam, has good solubility in water, and does not generate residue.

[0013] Prior art documents

[0014] Patent Literature

[0015] Patent Literature 1: Japanese Patent Application Laid-Open No. 5-9500

[0016] Patent Literature 2: Japanese Patent Application Laid-Open No. 8-507095

[0017] Patent Literature 3: Japanese Patent Application Laid-Open No. 62-177100

[0018] Patent Literature 4: Japanese Patent Application Laid-Open No. 6-313200

[0019] Patent Literature 5: Japanese Patent Application Laid-Open No. 53-26782

[0020] Patent Literature 6: Japanese Patent Application Laid-Open No. 2009-7566

[0021] Patent Literature 7: Japanese Patent Application Laid-Open (JP-A) No. 63-154798

[0022] Patent Literature 8: Japanese Patent Application Laid-Open (JP-A) No. 60-188498 SUMMARY

[0023] PROBLEMS TO BE SOLVED BY THE INVENTION

[0024] The present application provides a solid bleaching agent-containing substance having a coating layer and a cleaning agent composition incorporating the solid bleaching agent-containing substance having a coating layer. The solid bleaching agent-containing substance having a coating layer and the cleaning agent composition incorporating the solid bleaching agent-containing substance having a coating layer can be stabilized by preventing the solid bleaching agent from deteriorating, deactivating, and decomposing. In addition, an effect of generating only a small amount of foam or no foam can be obtained. Furthermore, an effect of having good water solubility, generating only a small amount of residue or no residue can be obtained.

[0025] MEANS FOR SOLVING THE PROBLEMS

[0026] The present inventors have intensively studied in view of the above problems, and as a result, have found that by selecting 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 dibasic carboxylic acid, an alkali metal salt of an acyclic monobasic carboxylic acid having 1 to 7 carbon atoms, and a mixture thereof (hereinafter, sometimes simply referred to as an alkali metal salt of a carboxylic acid) as a material for a coating layer, a solid bleaching agent-containing substance having a coating layer and a cleaning agent composition incorporating the same can be stabilized by preventing the solid bleaching agent from deteriorating, deactivating, and decomposing. In addition, the present inventors have found that the solid bleaching agent-containing substance can obtain an effect of generating only a small amount of foam or no foam. Furthermore, the present inventors have found that the solid bleaching agent-containing substance has good water solubility, and can obtain an effect of generating only a small amount of residue or no residue.

[0027] In addition, the present inventors have found that the alkali metal salt of an aromatic carboxylic acid, the alkali metal salt of an acyclic dibasic carboxylic acid, the alkali metal salt of an acyclic monobasic carboxylic acid having 1 to 7 carbon atoms, and the mixture thereof used as a coating layer stabilize the bleaching agent particles, and no inappropriate side reaction occurs between the solid bleaching agent and the coating layer, and thus the coating layer can be directly provided on the surface of the solid bleaching agent without providing an additional layer for separating the solid bleaching agent and the coating layer.

[0028] In the present application, "non-foaming" means that the amount of foam generated is none or very little when a water solution of the solid bleaching agent-containing substance having a coating layer adjusted to a certain concentration is mixed or stirred. "Good solubility in water and no residue generated" means that a water solution of the solid bleaching agent-containing substance having a coating layer adjusted to a certain concentration is clear and not turbid, and no insoluble matter (precipitate, float) is generated or very little is generated. In addition, "stabilization" means that, in comparison with a solid bleaching agent not having a coating layer, the deterioration, inactivation, decomposition of the solid bleaching agent is inhibited (reduced) in the case where the solid bleaching agent-containing substance having a coating layer is stored for a certain period of time.

[0029] The "alkali metal salt of carboxylic acid" in the present application means a salt in which a carboxyl group in a molecule is neutralized by an alkali metal. It can also be a salt in which not all of the carboxyl groups in the molecule are neutralized but some of them are neutralized.

[0030] The "solid state" in the present application means that it is in a solid state as long as it is in a solid state in the temperature range of use of the solid bleaching agent, and it can contain a compound having a melting point. In addition, it can contain a substance obtained by adsorbing a liquid on a known adsorbent or the like to make it powdery; a substance obtained by making an oil or a gel into a capsule shape.

[0031] In order to further improve the effects of cleaning, sterilization, bleaching, and the like, the solid bleaching agent-containing substance having a coating layer in the present application can be used in combination with a cleaning agent composition. In such a cleaning agent composition, various components such as an alkali agent, a chelating agent, a surfactant, and the like can be combined as components other than the solid bleaching agent.

[0032] That is, the present application relates to a solid bleaching agent-containing substance having a coating layer and a cleaning agent composition in which the solid bleaching agent-containing substance having a coating layer is combined.

[0033] Item 1. A solid bleaching agent-containing substance having a first layer containing a solid bleaching agent and a second layer containing a coating layer, wherein the coating layer contains 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 dibasic carboxylic acid, an alkali metal salt of an acyclic monobasic carboxylic acid having 1 to 7 carbon atoms, and a mixture thereof.

[0034] Item 2. The solid bleaching agent-containing substance according to item 1, wherein the alkali metal salt of an aromatic carboxylic acid is one or more selected from the group consisting of alkali metal salts of benzoic acid, o-phthalic acid, m-phthalic acid, p-phthalic acid, trimellitic acid, and p-t-butylbenzoic acid, and a mixture thereof.

[0035] Item 3 The solid bleaching agent containing matter according to item 1, wherein the alkali metal salt of non-cyclic dicarboxylic acid is one or more selected from the group consisting of alkali metal salts of succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid and tetradecanedioic acid, and a mixture thereof.

[0036] Item 4 The solid bleaching agent containing matter according to item 1, wherein the alkali metal salt of non-cyclic monocarboxylic acid having a carbon number of 1 to 7 is one or more selected from the group consisting of alkali metal salts of formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid and enanthic acid, and a mixture thereof.

[0037] Item 5 The solid bleaching agent containing matter according to item 1, wherein the solid bleaching agent is one or more selected from the group consisting of halogen-containing bleaching agents, oxygen-containing bleaching agents and a mixture thereof.

[0038] Item 6 The solid bleaching agent containing matter according to item 5, wherein the halogen-containing bleaching agent is one or more selected from the group consisting of halogenated isocyanuric acid, alkali metal salt of halogenated isocyanuric acid, hydrate of alkali metal salt of halogenated isocyanuric acid, halogenated hydantoin, metal hypochlorite and a mixture thereof.

[0039] Item 7 The solid bleaching agent containing matter according to item 5, wherein the oxygen-containing bleaching agent is one or more selected from the group consisting of percarbonate, perborate, peroxysulfate and a mixture thereof.

[0040] Item 8 A cleaning agent composition formed by compounding the solid bleaching agent containing matter according to item 1 with one or more metal ion capturing agents selected from the group consisting of aminocarboxylate, hydrate of aminocarboxylate, hydroxaminocarboxylate, hydrate of hydroxaminocarboxylate and a mixture thereof.

[0041] Item 9 A cleaning agent composition formed by compounding the solid bleaching agent containing matter according to item 1 with one or more non-ionic surfactants.

[0042] Item 10 A cleaning agent composition formed by compounding the solid bleaching agent containing matter according to item 1 with one or more alkali metal salts selected from the group consisting of alkali metal hydroxide, alkali metal silicate, alkali metal carbonate, alkali metal phosphate and a mixture thereof.

[0043] Effects of the Invention

[0044] The solid bleaching agent-containing substance with a coating layer according to the present application, when a solid bleaching agent is used for the purpose of cleaning, sterilizing, bleaching, etc. in order to clean a drain, a water storage portion, etc. of a kitchen, a bathroom, a washroom, a toilet, etc.; to wash laundry, etc.; to clean tableware, cooking utensils; to keep bath water, pool water, etc. clean, not only improves the deterioration, inactivation, decomposition of the bleaching agent in the case of being mixed with various surfactants, alkali agents, metal ion capturing agents, etc. as components for improving the effects of cleaning, sterilizing, bleaching, etc., but also simultaneously improves the deterioration, decomposition of various compounds mixed with the bleaching agent. In addition, the solid bleaching agent-containing substance can achieve the effects of generating little or no foam, and can achieve the effects of good solubility in water, generating little or no residue, and thus can be used for a wide range of purposes. Further, it has the following characteristics: since the bleaching agent particles are protected by the coating layer, the solid bleaching agent is prevented from coming into contact with other compounds, and thus no undesirable side reactions such as deterioration, inactivation, decomposition, etc. occur between the solid bleaching agent and other compounds.

[0045] The solid bleaching agent-containing substance with a coating layer and the cleaning agent composition incorporating the same are stabilized by using 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 dibasic carboxylic acid, an alkali metal salt of an acyclic monobasic carboxylic acid having 1 to 7 carbon atoms, and a mixture thereof for the coating layer. Further, the coating layer formed by including any one or more selected from the group consisting of the alkali metal salt of the aromatic carboxylic acid, the alkali metal salt of the acyclic dibasic carboxylic acid, the alkali metal salt of the acyclic monobasic carboxylic acid having 1 to 7 carbon atoms, and the mixture thereof has the following characteristics: it is extremely stable even when coming into contact with the solid bleaching agent, and no undesirable side reactions occur between the solid bleaching agent and the coating layer, and thus the coating layer can be directly provided on the surface of the solid bleaching agent without providing an additional layer for separating the solid bleaching agent and the coating layer. It also has the following characteristics: when the coating layer is formed on the solid bleaching agent using any one or more selected from the group consisting of the alkali metal salt of the aromatic carboxylic acid, the alkali metal salt of the acyclic dibasic carboxylic acid, the alkali metal salt of the acyclic monobasic carboxylic acid having 1 to 7 carbon atoms, and the mixture thereof, the coating layer is not easily aggregated, and has excellent processability.

[0046] The solid bleaching agent is any one of a halogen-containing bleaching agent, an oxygen-containing bleaching agent, and a mixture thereof, and thus has excellent effects of cleaning, sterilizing, bleaching, etc.

[0047] Further, by the halogen-based bleaching agent being one or more selected from the group consisting of halogenated isocyanuric acid, alkali metal salt of halogenated isocyanuric acid, hydrate of alkali metal salt of halogenated isocyanuric acid, halogenated hydantoin, metal salt of hypochlorous acid, and a mixture thereof, and the oxygen-based bleaching agent being one or more selected from the group consisting of percarbonate, perborate, peroxysulfate, and a mixture thereof, the cleaning, sterilization, bleaching, and the like are excellent, and it is easy to obtain, the operability is excellent, and it can be implemented within an economically allowable range.

[0048] For the detergent composition of the present application in which the solid bleaching agent-containing substance having a coating layer is compounded, when the solid bleaching agent is used for the purpose of cleaning, sterilization, bleaching, and the like, in order to improve the effect of the detergent composition, in the case where various metal ion capturing agents including aminocarboxylate and a hydrate thereof and hydroxylaminocarboxylate and a hydrate thereof, various surfactants including a nonionic surfactant, various alkali agents including alkali metal hydroxide, alkali metal silicate, alkali metal carbonate, and alkali metal phosphate, and the like detergent ingredients are mixed, not only the problems of deterioration, inactivation, decomposition of the solid bleaching agent are improved, but also the problems of deterioration, decomposition of the metal ion capturing agent, the surfactant, the alkali agent, and the like as the detergent ingredients are improved. Therefore, the detergent composition has the following characteristics: even after a certain period of storage, preservation under severe conditions such as warming, humidification, and the like, the effect of the detergent composition on cleaning, sterilization, bleaching, and the like is also maintained at a high level. DETAILED DESCRIPTION

[0049] Hereinafter, the present application will be described in detail.

[0050] Note that in the present specification, "mass" and "weight" have the same meaning.

[0051] The solid bleaching agent-containing substance of the present application is characterized by having a first layer containing a solid bleaching agent and a second layer including a coating layer, the coating layer containing one or more selected from the group consisting of an alkali metal salt of aromatic carboxylic acid, an alkali metal salt of acyclic dibasic carboxylic acid, an alkali metal salt of acyclic monobasic carboxylic acid having 1 to 7 carbon atoms, and a mixture thereof.

[0052] The alkali metal salt of aromatic carboxylic acid in the present application can have one or more aromatic rings and one or more carboxyl groups in the molecule, and is an alkali metal salt of a carboxylic acid represented by the following Chemical Formula (I-1), (I-2), (I-3), or (I-4). Note that in the present specification, the case where "may have a substituent" includes, for example, the case where "does not have a substituent, and the carbon chain is a straight chain" and the case where "the carbon chain is branched".

[0053]

[0054] (In formula (I-1), R1, R2, R3, R4, R5 each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which can have a substituent, an aryl group having 6 to 14 carbon atoms which can have a substituent, an unsaturated hydrocarbon having 1 to 17 carbon atoms, an acyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxyl group, a hydroxyl group, a nitro group, an amino group, a sulfonic acid group, a mercapto group, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.)

[0055]

[0056] (In formula (I-2), R6, R7, R8, R9, R 10 each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which can have a substituent, an aryl group having 6 to 14 carbon atoms which can have a substituent, an unsaturated hydrocarbon having 1 to 17 carbon atoms, an acyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxyl group, a hydroxyl group, a nitro group, an amino group, a sulfonic acid group, a mercapto group, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. R 11 represents a methylene group, an alkylene group having 1 to 6 carbon atoms which can have a substituent, or an unsaturated hydrocarbon having 2 to 6 carbon atoms which can have a substituent.)

[0057]

[0058] (In formula (I-3), R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which can have a substituent, an aryl group having 6 to 14 carbon atoms which can have a substituent, an unsaturated hydrocarbon having 1 to 17 carbon atoms, an acyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxyl group, a hydroxyl group, a nitro group, an amino group, a sulfonic acid group, a mercapto group, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.)

[0059]

[0060] (In formula (I-4), R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which can have a substituent, an aryl group having 6 to 14 carbon atoms which can have a substituent, an unsaturated hydrocarbon having 1 to 17 carbon atoms, an acyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxyl group, a hydroxyl group, a nitro group, an amino group, a sulfonic acid group, a mercapto group, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

[0061] As the alkali metal salt of the aromatic carboxylic acid used in the present application, one or more selected from the group consisting of alkali metal salts of benzoic acid, salicylic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, cinnamic acid, o-toluic acid, m-toluic acid, p-toluic acid, phthalic acid, isophthalic acid, terephthalic acid, phenylacetic acid, 2-phenylpropionic acid, phenoxyacetic acid, phenylpyruvic acid, o-tert-butylbenzoic acid, m-tert-butylbenzoic acid, p-tert-butylbenzoic acid, 3,5-di-tert-butylbenzoic acid, 3,5-di-tert-butylsalicylic acid, o-benzoylbenzoic acid, m-benzoylbenzoic acid, p-benzoylbenzoic acid, o-aminobenzoic acid, 1-naphthoic acid, 2-naphthoic acid, 1,2-naphthalene dicarboxylic acid, 2,3-naphthalene dicarboxylic acid, 3-hydroxy-2-naphthoic acid, 2-hydroxyphenylacetic acid, 3-hydroxyphenylacetic acid, 4-hydroxyphenylacetic acid, D-mandelic acid, L-mandelic acid, trimellitic acid, pyromellitic acid, 2-methoxyphenylacetic acid, 3-methoxyphenylacetic acid, and 4-methoxyphenylacetic acid, and a mixture thereof, and the like are preferred.

[0062] From the viewpoints of availability, safety, non-reactivity with the solid bleaching agent, ease of formation of the coated layer, and stability of the solid bleaching agent content in combination with the cleaning agent composition, the alkali metal salt of the aromatic carboxylic acid is more preferably one or more selected from the group consisting of alkali metal salts of benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, and p-tert-butylbenzoic acid, and a mixture thereof.

[0063] As the metal salt, an alkali metal salt such as a lithium salt, a sodium salt, a potassium salt, and the like, an alkaline earth metal salt such as a calcium salt, and the like can be used. From the viewpoint of availability, an alkali metal salt is preferred, and from the viewpoint of solubility in water, a sodium salt and a potassium salt are further preferred.

[0064] The alkali metal salt of the acyclic dicarboxylic acid in the present application is one represented by Chemical Formula (II-1) or Chemical Formula (II-2) as long as it has an acyclic hydrocarbon chain which can have a substituent and at least two carboxyl groups.

[0065]

[0066] (In Chemical Formula (II-1), R 26 represents an alkylene group having 1 to 34 carbon atoms which can have a substituent or an acyclic unsaturated hydrocarbon having 1 to 34 carbon atoms which can have a substituent.

[0067]

[0068] As the alkali metal salt of the noncyclic dicarboxylic acid used in the present application, one or more selected from the group consisting of alkali 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 are preferable.

[0069] From the viewpoints of availability and safety, the alkali metal salt of the noncyclic dicarboxylic acid is more preferably one or more selected from the group consisting of alkali metal salts of succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, and tetradecanedioic acid, and mixtures thereof.

[0070] As the metal salt, alkali metal salts such as lithium salts, sodium salts, potassium salts, and the like, and alkaline earth metal salts such as calcium salts, and the like can be used. From the viewpoint of availability, an alkali metal salt is preferable, and from the viewpoint of solubility in water, a sodium salt, a potassium salt is further preferable.

[0071] The alkali metal salt of the noncyclic monocarboxylic acid having 1 to 7 carbon atoms in the present application is one that has a noncyclic hydrocarbon chain that can have a substituent and 1 carboxyl group and the total number of carbon atoms in the molecule is 1 to 7, and is an alkali metal salt of a carboxylic acid represented by the following formula (III).

[0072]

[0073] (In formula (III), R 27 represents a hydrogen atom, a noncyclic alkyl group having 1 to 6 carbon atoms that can have a substituent, or a noncyclic unsaturated hydrocarbon having 1 to 6 carbon atoms that can have a substituent.)

[0074] As the alkali metal salt of the noncyclic monocarboxylic acid having 1 to 7 carbon atoms used in the present application, one or more selected from the group consisting of alkali metal salts of formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid (caprylic acid), heptanoic acid (coniferyl acid), acrylic acid, methacrylic acid, isobutyric acid, and isovaleric acid, and mixtures thereof are preferable.

[0075] From the viewpoint of easy availability, the alkali metal salt of the noncyclic monocarboxylic acid having 1 to 7 carbon atoms is more preferably one or more selected from the group consisting of alkali metal salts of formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, and heptanoic acid, and a mixture thereof. Further, from the viewpoints of non-reactivity with the solid bleaching agent and non-aggregatability at the time of processing, it is further preferable to be one or more selected from the group consisting of alkali metal salts of propionic acid, butyric acid, and valeric acid having 3 to 5 carbon atoms, and a mixture thereof.

[0076] As the metal salt, an alkali metal salt such as a lithium salt, a sodium salt, a potassium salt, and an alkaline earth metal salt such as a calcium salt can be used. From the viewpoint of easy availability, an alkali metal salt is preferable, and from the viewpoint of solubility in water, a sodium salt and a potassium salt are further preferable.

[0077] The alkali metal salt of the carboxylic acid used in the present application can use an alkali metal salt of a carboxylic acid that has been previously neutralized, or can be produced by neutralizing a carboxylic acid with an alkali metal. As a method of neutralizing a carboxylic acid with an alkali metal, it can be produced by dissolving a carboxylic acid in an aqueous solution of an alkali metal hydroxide or the like.

[0078] For example, in the case of producing an alkali metal salt of a dibasic carboxylic acid having 2 carboxyl groups within a molecule, a sodium salt of a dibasic carboxylic acid in which one of the 2 carboxyl groups within a molecule is neutralized with sodium can be obtained by dissolving a dibasic carboxylic acid in water in which sodium hydroxide corresponding to the molar equivalent of the dibasic carboxylic acid has been previously dissolved. In addition, if sodium hydroxide corresponding to twice the molar equivalent of the dibasic carboxylic acid is used, a sodium salt of a dibasic carboxylic acid in which both of the 2 carboxyl groups within a molecule are neutralized with sodium can be obtained.

[0079] The solid bleaching agent used in the present application is preferably one or more selected from the group consisting of halogen-containing bleaching agents, oxygen-containing bleaching agents, and a mixture thereof.

[0080] As the halogen-containing bleaching agent, one or more selected from the group consisting of halogenated isocyanuric acid, an alkali metal salt of halogenated isocyanuric acid, a hydrate of an alkali metal salt of halogenated isocyanuric acid, halogenated hydantoin, a metal salt of hypochlorous acid, and a mixture thereof can be exemplified.

[0081] As the halogenated isocyanuric acid, an alkali metal salt of halogenated isocyanuric acid, and a hydrate of an alkali metal salt of halogenated isocyanuric acid, one or more selected from the group consisting of trichloroisocyanuric acid, sodium dichloroisocyanurate, a hydrate of sodium dichloroisocyanurate, potassium dichloroisocyanurate, and a mixture thereof is preferable, and one or more selected from the group consisting of trichloroisocyanuric acid, sodium dichloroisocyanurate, a hydrate of sodium dichloroisocyanurate, and a mixture thereof is more preferable from the viewpoints of easy availability and safety.

[0082] As the halogenated hydantoin, 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 a mixture thereof are preferred. Note that 1-bromo-3-chloro-5,5-dimethylhydantoin and 1-chloro-3-bromo-5,5-dimethylhydantoin are sometimes collectively referred to as bromochloro-5,5-dimethylhydantoin.

[0083] As the metal hypochlorite, calcium hypochlorite (bleaching powder) is preferred.

[0084] As the oxygen-containing bleaching agent, organic peroxides including percarbonate, perborate, peroxymonosulfate, perbenzoic acid, and the like can be exemplified. As the percarbonate, sodium carbonate peroxohydrogen adduct (sometimes referred to simply as sodium percarbonate) in which hydrogen peroxide is added to sodium carbonate can be exemplified. As the perborate, sodium perborate can be exemplified. As the peroxymonosulfate, peroxymonosulfuric acid-sulfuric acid-pentapotassium salt, potassium peroxodisulfate salt, and a mixture thereof can be exemplified.

[0085] From the viewpoints of easy availability and easy handleability, as the oxygen-containing bleaching agent, one or more selected from the group consisting of sodium percarbonate, sodium perborate, peroxymonosulfuric acid-sulfuric acid-pentapotassium salt, and a mixture thereof is preferred.

[0086] In comparison with the conventional solid bleaching agent, the solid bleaching agent containing body having a coating layer in the present application is stabilized by having a coating layer, and thus can be formulated with a wider range of compound groups (detergent ingredients) to make a detergent composition, and thus used for cleaning, sterilization, bleaching, and the like. As these compound groups, one or more selected from the group consisting of an organic substance, an inorganic substance, and a mixture thereof can be used. In the case of using as a mixture, it can be used after a molding step, or directly used. In the case of passing through a molding step, it can be used in any size and dosage form such as a powder, a granule, a tablet, an extrusion molded product, an injection molded cured product, a slurry, and the like.

[0087] In addition, as to the solid bleaching agent containing body having a coating layer of the present application, one or more selected from the group consisting of the organic substance, the inorganic substance, and the mixture thereof can be contained in the coating layer as an additive, or in the solid bleaching agent, within a range not impairing the effects of the present application. Further, a multilayer coating film can be formed as a layer different from the coating layer of the present application.

[0088] As the organic substance, an organic acid, an organic polymer, a surfactant, a rinse agent, an antifoaming agent, a metal ion capturing agent, a pigment, a perfume, an enzyme, and the like can be exemplified.

[0089] As the organic acid, aromatic carboxylic acid, acyclic carboxylic acid can be used. However, in the case where a compound having a large molecular weight and low solubility in water is used, it is preferable to limit the use to a small amount within a range not impairing the effect of the present application (an effect of obtaining a good solubility in water and generating only a small amount of residue or no residue). In the case where a compound having a large molecular weight and low solubility in water is used, measures such as increasing the solubility in water by using in combination with an alkali metal hydroxide, an alkali metal salt and making the carboxylic acid into an alkali metal salt can be taken.

[0090] As such an organic acid, for example, benzoic acid, salicylic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, cinnamic acid, o-toluic acid, m-toluic acid, p-toluic acid, phthalic acid, isophthalic acid, terephthalic acid, phenylacetic acid, 2-phenylpropionic acid, phenoxyacetic acid, phenylpyruvic acid, o-tert-butylbenzoic acid, m-tert-butylbenzoic acid, p-tert-butylbenzoic acid, 3,5-di-tert-butylbenzoic acid, 3,5-di-tert-butylsalicylic acid, o-benzoylbenzoic acid, m-benzoylbenzoic acid, p-benzoylbenzoic acid, o-aminobenzoic acid, 1-naphthoic acid, 2-naphthoic acid, 1,2-naphthalene dicarboxylic acid, 2,3-naphthalene dicarboxylic acid, 3-hydroxy-2-naphthoic acid, 2-hydroxyphenylacetic acid, 3-hydroxyphenylacetic acid, 4-hydroxyphenylacetic acid, D-mandelic acid, L-mandelic acid, trimellitic acid, pyromellitic acid, 2-methoxyphenylacetic acid, 3-methoxyphenylacetic acid, 4-methoxyphenylacetic acid, 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, undecanedioic acid, dodecanedioic acid, tetradecanedioic acid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tetradecanoic acid, octadecanoic acid, hexadecanoic acid, and the like can be exemplified.

[0091] As the organic polymer, polysaccharides such as carrageenan, guar gum, locust bean gum, alginic acid, alkali metal salts of alginic acid, dextrin, xanthan gum, pectin, starch or derivatives thereof, methyl cellulose, carboxymethyl cellulose, alkali metal salts of carboxymethyl cellulose, ethyl cellulose, hydroxypropyl cellulose, hydroxyethyl cellulose, other cellulose derivatives, and the like can be exemplified. Alternatively, synthetic high molecular compounds such as polyvinyl alcohol, polyacrylamide, polyethylene glycol, polyacrylic acid, olefin-maleic anhydride sodium salt copolymer, acrylic acid-maleic acid sodium salt copolymer, diallyldimethylammonium-acrylic acid sodium salt copolymer, diallylmethylamine-maleic acid sodium salt copolymer, and the like can be exemplified.

[0092] As the surfactant, anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, and mixtures thereof can be exemplified, and a surfactant having less foaming can be preferably used. In the case where a surfactant having strong foaming is added, it is preferable to limit the addition to a small amount or to take measures such as adding an antifoaming agent which inhibits foaming, within a range where the effect of the present application is not impaired (an effect where only a small amount of foaming or no foaming occurs can be obtained). Among them, from the viewpoints of easiness of availability, easiness of handling, and low foaming, it is preferable to use one or more nonionic surfactants.

[0093] As the anionic surfactant, potassium oleate soap, potassium castor oil soap, semi-solidified sodium tallow fatty acid soap, semi-solidified potassium tallow fatty acid soap, and the like can be exemplified. As the alkyl sulfate salt, sodium dodecyl sulfate, sodium higher alcohol sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, and the like can be exemplified. As the alkylbenzenesulfonic acid salt, sodium dodecylbenzenesulfonate, and the like can be exemplified. As the alkylnaphthalenesulfonic acid salt, sodium alkylnaphthalenesulfonate, and the like can be exemplified. As the dialkylsulfosuccinic acid salt, sodium dialkylsulfosuccinate, and the like can be exemplified. As the alkylarylether sulfonic acid salt, sodium alkylarylether sulfonate, and the like can be exemplified. As the alkylphosphoric acid salt, potassium alkylphosphonate, and the like can be exemplified. As the naphthalenesulfonic acid formalin condensate, sodium salt of β-naphthalenesulfonic acid formalin condensate, and the like can be exemplified. As the aromatic sulfonic acid formalin condensate, sodium salt of aromatic sulfonic acid formalin condensate, and the like can be exemplified. As the polyoxyethylene alkyl ether sulfate salt, sodium polyoxyethylene dodecyl ether sulfate, and the like can be exemplified. As the alkylsulfosuccinic acid salt, sodium alkylsulfosuccinate, and the like can be exemplified.

[0094] As the cationic surfactant, coconut amine acetate, stearyl amine acetate, and the like can be exemplified. As the quaternary ammonium salt, lauryl trimethylammonium salt, stearyl trimethylammonium salt, distearyl dimethylammonium salt, alkylbenzyl dimethylammonium salt, cetyl trimethylammonium salt, stearyl trimethylammonium salt, behenyl trimethylammonium salt, distearyl dimethylammonium salt, diisotetradecyl dimethylammonium salt, and the like can be exemplified.

[0095] As the nonionic surfactant, there can be mentioned polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene higher alcohol ether, and the like; sorbitan laurate, sorbitan palmitate, sorbitan stearate, sorbitan oleate, and the like; polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan stearate, polyoxyethylene sorbitan oleate, and the like; polyethylene glycol laurate, polyethylene glycol stearate, polyethylene glycol oleate, and the like; polyoxyethylene lauryl amine, polyoxyethylene stearyl amine, ethylenediamine-polyoxyethylene-polyoxypropylene block polymer, and the like; lauric acid monoethanolamide, lauric acid diethanolamide, myristic acid monoethanolamide, myristic acid diethanolamide, stearic acid monoethanolamide, stearic acid diethanolamide, coconut oil fatty acid monoethanolamide, coconut oil fatty acid diethanolamide, and the like; stearic acid monoglyceride, stearic acid diglyceride, palmitic acid monoglyceride, palmitic acid diglyceride, oleic acid monoglyceride, oleic acid diglyceride, and the like; sucrose fatty acid ester, and the like.

[0096] As the amphoteric surfactant, there can be mentioned lauryl betaine, stearyl betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazoline alkyl betaine, such as betaine; amine oxide, such as lauryl dimethyl amine oxide, and the like.

[0097] For a dish washing machine used in a kitchen for work in a restaurant or the like, a rinse agent is used in order to accelerate drying of dishes in a rinsing process and to reduce white spots called water spots, thereby treating with good appearance. As such a rinse agent, the nonionic surfactant, the organic high polymer, and other rinse agents can be used.

[0098] As the defoaming agent, various defoaming agents such as polysiloxane-based, mineral oil-based, and polyether-based defoaming agents can be exemplified. These defoaming agents are sold on the market in the form of a liquid, a solid, an emulsion, or the like. As the polysiloxane-based defoaming agent, KM-89, KM-7750, KM-7752 (all are trade names, manufactured by Shin-Etsu Chemical Co., Ltd.), Anti-form (registered trademark) E20 (all are trade names, manufactured by Kawabata Kagaku Co., Ltd.), TSA780, TSA739, YSA6406, YMA6509 (all are trade names, manufactured by Momentive Performance Materials Japan Co., Ltd.), and the like can be exemplified. As the mineral oil-based defoaming agent, Nopco (registered trademark) 8034, SN Defoamer VL, SN Defoamer 269, Nopco 267A (all are trade names, manufactured by Sankyo-Peco Co., Ltd.), and the like can be exemplified. As the polyether-based defoaming agent, SN Defoamer 470, SN Defoamer 14HP (all are trade names, manufactured by Sankyo-Peco Co., Ltd.), and the like can be exemplified. In addition to these, defoaming agents described in, for example, "Application of Defoaming Agents" (CMC Co., Ltd., supervised by Hikotaka Sasaki, first edition, first printing, published on May 30, 1991) can be used.

[0099] As the metal ion capturing agent, aminocarboxylate salts such as nitrilotriacetate, ethylenediaminetetraacetate, beta-alaninediacetate, asparticdicaetate, methylglycinediacetate, and iminodisuccinate, and hydrates thereof; hydroxamino carboxylate salts such as serinediacetate, hydroxyiminodisuccinate, hydroxyethylethylenediaminetriacetate, and dihydroxyglycinate, and hydrates thereof; phosphonocarboxylic acids such as tripolyphosphate, 1-diphosphonic acid, alpha-methylphosphonobutandioic acid, and 2-phosphonobutane-1,2-dicarboxylic acid, alkali metal salts thereof, and hydrates thereof; polyacrylic acid and alkali metal salts thereof; glutamicdicaetate and hydrates thereof, and the like can be exemplified. Among these, from the viewpoints of easy availability, easy handling, and metal ion removal effect, one or more metal ion capturing agents selected from the group consisting of aminocarboxylate salts, hydrates of aminocarboxylate salts, hydroxamino carboxylate salts, hydrates of hydroxamino carboxylate salts, and a mixture thereof are preferably used.

[0100] As the pigment, Scarlet G conc, Permanent Red GY, Seika Fast (registered trademark) Carmine 3870, Seika Fast Yellow 2200, Seika Fast Yellow 2700(B) (trade names, manufactured by Otsuka Chemical Co., Ltd.), Acid Blue 9, Direct Yellow 12 (trade names, manufactured by Tokyo Chemical Industry Co., Ltd.), Phthalocyanine Blue, Riboflavin (trade names, manufactured by Wako Pure Chemical Industries, Ltd.), Ultramarine Blue (trade names, manufactured by Nippon Kayaku Co., Ltd.), and the like can be exemplified.

[0101] As the perfume, a perfume known in the past can be used.

[0102] As the enzyme, various enzymes useful for cleaning can be used.

[0103] As the inorganic substance, silicates, carbonates, sulfates, phosphates, acetates, hydroxides of alkali metals, chlorides of alkali metals, aluminum sulfates, silicones, and the like can be exemplified. From the viewpoints of easy availability, easy solubility in water, and easy handleability, silicates, carbonates, phosphates, hydroxides of alkali metals are more preferable.

[0104] As the silicates, sodium silicate, sodium metasilicate, sodium orthosilicate, hydrates thereof, and mixtures thereof, and the like can be exemplified. As the carbonates, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, sodium sesquicarbonate, and the like can be exemplified. As the sulfates, sodium sulfate, potassium sulfate, and the like can be exemplified. As the phosphates, sodium dihydrogen phosphate, potassium dihydrogen phosphate, sodium tripolyphosphate, and the like can be exemplified. As the hydroxides of alkali metals, sodium hydroxide, potassium hydroxide, lithium hydroxide, and the like can be exemplified. As the chlorides of alkali metals, sodium chloride, potassium chloride, and the like can be exemplified. As the silicones, dimethylpolysiloxane, and the like can be exemplified. Among them, from the viewpoints of easy availability, easy handleability, and strength of alkalinity, it is preferable to use one or more alkali metal salts selected from the group consisting of hydroxides of alkali metals, silicates of alkali metals, carbonates of alkali metals, phosphates of alkali metals, and mixtures thereof.

[0105] The solid bleaching agent-containing product of the present application can be in any form such as powder, granules, tablets, etc., but from the viewpoint of workability in the case of use as a raw material for a detergent composition, powder and granules are preferred. The shape of the solid bleaching agent-containing product of the present application is not particularly limited and can be any shape such as spherical, cylindrical, conical, other polyhedral, needle-shaped, etc., or a mixture of these shapes. In addition, in the production of the solid bleaching agent-containing product of the present application, a powder, granules, an extrusion-molded product obtained using a chilsonator or the like, a crushed product of the extrusion-molded product, a solid bleaching agent obtained by previously performing processing such as tabletting or granulation, etc., can be used as a raw material, and the solid bleaching agent can contain an additive.

[0106] In the case where the solid bleaching agent-containing product of the present application is powder or granules, the average particle diameter is not particularly limited and is preferably in the range of 1 μm to 5000 μm, more preferably 10 μm to 3000 μm, and further preferably 100 μm to 1500 μm. In the case where the solid bleaching agent-containing product is used as a raw material for incorporation into a detergent or the like, in the case where the average particle diameter is 5000 μm or less, the particles are not too large and workability is good, in the case where it is 3000 μm or less, workability is even better, and in the case where it is 1500 μm or less, workability is further better. In addition, in the case where the average particle diameter is 5000 μm or less, even in the case of direct use for cleaning and bleaching, it can be directly put into a drain or the like having a small opening, and thus use is easy, in the case where it is 3000 μm or less, use is even easier, and in the case where it is 1500 μm or less, use is further easier. On the other hand, if the average particle diameter is 1 μm or more, the particles are less likely to scatter due to a slight breeze or static electricity during handling, and thus use is easy, in the case where it is 10 μm or more, use is even easier, and in the case where it is 100 μm or more, use is further easier.

[0107] The average particle size can be determined as follows. A 13-stage sieve with mesh sizes 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, 2000 μm and a tray are used, and the sieves are stacked on the tray in order of the mesh size from the largest to the smallest. The test sample is placed on the uppermost sieve with a mesh size of 2000 μm, and the stacked sieves are supported with one hand and tapped at a rate of about 120 times per minute. The sieves are occasionally placed horizontally, and the sieve frame is tapped several times strongly. This operation is repeated, and the sieving is performed sufficiently. In the case where the test sample is aggregated due to static electricity or the like, or in the case where fine powder is attached to the inner side or back of the sieve, the test sample is gently dispersed with a brush, and the sieving operation is performed again. The test sample that has passed through the sieve is collected as undersize. Note that the undersize refers to the test sample that has passed through the sieve at the end of the sieving. In the case where the test sample contains particles having a particle size of more than 2000 μm, a sieve having a mesh size of 2360 μm, 2800 μm, 3350 μm, 4000 μm, 4750 μm, 5600 μm or more can be added, and in the case where the test sample contains many particles having a particle size of 75 μm or less, a sieve having a mesh size of 63 μm, 53 μm, 45 μm, 38 μm or less can be added.

[0108] The mass of the particles remaining on each sieve and tray is determined, and the mass ratio (%) of the particles on each sieve is calculated. The mass ratios of the particles on the sieves with smaller mesh sizes are added sequentially from the tray to be accumulated. In the case where the mesh size of the initial sieve at which the accumulated mass ratio reaches 50% or more is set to a μm, the mesh size of the sieve one stage larger than a μm is set to b μm, the mass ratio of the sieve from the tray to a μm is set to c%, and the mass ratio on the sieve of a μm is set to d%, the average particle size is calculated from the following Formula 1.

[0109]

[0110] In the case where the solid bleaching agent-containing product of the present application is a tablet, there is no particular limitation, but a cylindrical shape or a straw-bundle shape can be used. In the case of a cylindrical shape, the diameter is preferably 5 mm to 2000 mm from the viewpoint of ease of processing and strength, and more preferably 5 mm to 500 mm from the viewpoint of operability. The height of the tablet is preferably 0.5 mm to 2000 mm, and more preferably 0.5 mm to 500 mm. In addition, the value obtained by dividing the diameter (mm) of the tablet by the height (mm) of the tablet is preferably in the range of 1.0 to 10.0. When the diameter and height of the tablet are in the predetermined range, the tablet is not too large and is easy to process. When the value obtained by dividing the diameter (mm) of the tablet by the height (mm) of the tablet is in the predetermined range, the tablet is not easily broken or damaged.

[0111] The solid bleaching agent-containing article of the present application can be produced by forming a coating layer on the solid bleaching agent. The production method is not particularly limited, and known methods such as a stirring method, a rotating method, a fluidized bed method, or the like can be used, or they can be used in combination. In the case of using the stirring method, the solid bleaching agent is fluidized by stirring with a stirring blade, and a liquid containing the coating layer component (hereinafter referred to as coating liquid) is added or sprayed, and a volatile component is removed as necessary using a drying means such as heating, thereby forming a coating layer. In the case of using the rotating method, the solid bleaching agent is put into a cylindrical treatment layer and rotated to fluidize the solid bleaching agent, and the coating liquid is added or sprayed, and a volatile component is removed as necessary using a drying means such as heating, thereby forming a coating layer. In the case of using the fluidized bed method, the solid bleaching agent in the treatment layer is fluidized using an air blower or the like, and the coating liquid is added or sprayed, and a volatile component is removed as necessary using a drying means such as heating, thereby forming a coating layer.

[0112] In producing the solid bleaching agent-containing article of the present application having a coating layer, a step of keeping the solid bleaching agent in a fluidized state and bringing the coating liquid into contact with the solid bleaching agent to thereby wet the solid bleaching agent, and a step of forming a coating layer on the surface of the solid bleaching agent by drying the solid bleaching agent in contact with the coating liquid can be included. The solid bleaching agent-containing article obtained by this production method has a coating layer formed on the outside of the solid bleaching agent serving as a core, and the solid bleaching agent is stabilized by the coating layer from various factors that cause deterioration, inactivation, or decomposition of the solid bleaching agent. The coating layer can be formed so as to completely cover the solid bleaching agent, or can be formed locally within a range that does not impair the effects of the present application.

[0113] The step of wetting the solid bleaching agent and the step of performing drying can be performed simultaneously or alternately and repeatedly. From the viewpoint of quickly completing the steps, simultaneous performance is more preferable.

[0114] The coating liquid can be prepared by mixing one or more solutes (hereinafter, sometimes collectively referred to as coating materials) selected from the group consisting of the compounds contained in the coating layer, additives, and mixtures thereof, and a solvent. The form of the coating liquid can be a solution state in which the coating materials are completely dissolved in the solvent, or a state in which a slurry or a solute is dispersed by swelling. As the solvent, one or more selected from the group consisting of organic solvents such as methanol, ethanol, propanol, 2-propanol, butanol, acetone, methyl ethyl ketone, ethyl acetate, tetrahydrofuran, toluene, and the like, water, and mixtures thereof are preferable from the viewpoints of easy availability and easy handling. Water, methanol, ethanol, and mixtures thereof are more preferable because they moderately dissolve the coating materials, and are removed quickly after wetting the solid bleaching agent, and water is further preferable from the viewpoints of safety in handling and easy availability.

[0115] In addition, in the case where the coating material has a melting point, it is possible to use the coating material in a molten state by warming to a temperature higher than the melting point. At this time, if a solvent is not used, it is possible to omit the process of drying the solid bleaching agent, and by cooling to a temperature lower than the melting point, the coating material in a molten state solidifies, and it is possible to easily form a coating layer, and thus this is preferred.

[0116] The method of bringing the coating liquid into contact with the solid bleaching agent is not particularly limited. For example, it is possible to spray the coating liquid onto the solid bleaching agent using a sprayer, or it is possible to directly drop the coating liquid onto the solid bleaching agent. From the viewpoint of uniformly bringing the coating liquid into contact, the method of spraying the coating liquid using a sprayer is preferred.

[0117] The sprayer nozzle used in the operation of the sprayer is not particularly limited, and a two-fluid nozzle is preferred.

[0118] In the case where the solvent such as water used in the manufacturing method of the solid bleaching agent-containing article is not completely removed through the drying process, in the case where moisture in the atmosphere is absorbed into the solid bleaching agent, and the like, the solid bleaching agent-containing article having a coating layer sometimes contains a trace amount of a volatile component. Such a volatile component can be removed by further performing drying.

[0119] In the case where the volatile component is water, the water content (mass %) in the solid bleaching agent-containing article is defined by the amount of mass reduction when drying is performed in a constant-temperature drier set to a temperature of 110°C, which is slightly higher than the boiling point of water, until a constant amount is reached, and is represented by the following Equation 2.

[0120] Water content (mass %) = (W2 - W1) x 100 / W2 (Equation 2)

[0121] W1: mass (g) of the sample after drying

[0122] W2: mass (g) of the sample before drying

[0123] The water content of the solid bleaching agent-containing article of the present application is not particularly limited, and is preferably 30 mass % or less, more preferably 10 mass % or less, and further preferably 5 mass % or less. In the case where the water content is small, it is possible to increase the content of the solid bleaching agent per unit mass in the solid bleaching agent-containing article, and thus this is advantageous. Therefore, it is preferred to provide a drying process after manufacturing. For example, in the case where water is used as the solvent, and drying is performed at a temperature of 110°C until a constant amount is reached, it is possible to consider that the water content becomes approximately 0 mass %.

[0124] In the case where the volatile component is a substance other than water, the temperature at which the volatile component can be sufficiently dried is not particularly limited as long as it is the same as described above, and the volatile component content is defined by the mass reduction amount when drying is performed in a constant temperature drier until a constant amount is reached, and can be calculated in the same manner as in the case of Equation 2. Note that the temperature at this time should be set to a temperature lower than the temperature at which the solid bleaching agent, coating material, or other additive other than the solvent decomposes, evaporates, or sublimates.

[0125] In the case where the solid bleaching agent is a chlorine-containing bleaching agent, the effective chlorine content (Cl2 conversion value) in the solid bleaching agent content can be calculated using iodine titration and according to Equation 3. That is, iodine liberated by the reaction of active chlorine with potassium iodide is titrated with a sodium thiosulfate solution, and the effective chlorine content is calculated according to the following Equation 3.

[0126] Effective chlorine content (%) = a x f x 0.35452 / b (Equation 3)

[0127] a: 0.1 N sodium thiosulfate solution required for titration (ml)

[0128] b: sample (g)

[0129] f: factor of 0.1 N sodium thiosulfate solution

[0130] Note that the theoretical effective chlorine content of trichloroisocyanuric acid is 91.53%, that of sodium dichloroisocyanurate is 64.48%, and that of sodium dichloroisocyanurate 2 hydrate is 55.40%.

[0131] In the case where the solid bleaching agent is an oxygen-containing type, the effective oxygen content (O2 conversion value) in the solid bleaching agent content can also be calculated using iodine titration. That is, iodine liberated by the reaction of active oxygen with potassium iodide is titrated with a sodium thiosulfate solution, and the effective oxygen content is calculated according to the following Equation 4. In order to accelerate the reaction of active oxygen with potassium iodide, a small amount of an ammonium molybdate aqueous solution adjusted to 1 mass% can also be added.

[0132] Effective oxygen content (%) = a x f x 0.08000 / b (Equation 4)

[0133] a: 0.1 N sodium thiosulfate solution required for titration (ml)

[0134] b: sample (g)

[0135] f: factor of 0.1 N sodium thiosulfate solution

[0136] For the solid bleaching agent-containing article of the present application, the proportion (mass ratio) of the layer containing the solid bleaching agent to the coating layer can be appropriately adjusted. The smaller the proportion of the coating layer, the larger the proportion of the solid bleaching agent, and thus it is advantageous from the viewpoint of maintaining the sterilizing, bleaching, cleaning, and the like functions of the solid bleaching agent. On the other hand, in the case where a cleaning agent composition is produced by combining the solid bleaching agent-containing article with various cleaning agent components, the larger the proportion of the coating layer, the further improved the stability.

[0137] Thus, the proportion of the coating layer formed on the solid bleaching agent is preferably within a certain range from the viewpoint of the proportion of the solid bleaching agent and the viewpoint of improved stability. From the viewpoint of the proportion of the solid bleaching agent, the upper limit of the proportion of the coating layer in the solid bleaching agent-containing article is preferably 50 mass% or less, more preferably 40 mass% or less, and further preferably 35 mass% or less. On the other hand, from the viewpoint of improved stability, the lower limit of the proportion of the coating layer in the solid bleaching agent-containing article is not particularly limited as long as the stability is improved, and is preferably 5 mass% or more, more preferably 10 mass% or more, and further preferably 20 mass% or more.

[0138] In the case where the solid bleaching agent is a chlorine-containing bleaching agent, the proportion of the coating layer in the solid bleaching agent-containing article of the present application can be calculated from the available chlorine content of the solid bleaching agent-containing article according to the following Formula 5. Note that in the case where the solid bleaching agent-containing article having a coating layer of the present application contains a solvent, the solvent content can be calculated in advance according to the above Formula 2, and the calculation according to Formula 5 is performed after subtracting the solvent content. Similarly, in the case where the solid bleaching agent is an oxygen-containing bleaching agent, the proportion of the coating layer can be calculated from the available oxygen content instead of the available chlorine content.

[0139] Proportion of coating layer (mass%) = (P1 - P2) x 100 / P1 (Formula 5)

[0140] P1: Available chlorine or available oxygen content (mass%) of the solid bleaching agent used as a raw material

[0141] P2: Available chlorine or available oxygen content (mass%) in the solid bleaching agent-containing article having a coating layer

[0142] In order to calculate the proportion of the coating layer in the solid bleaching agent-containing article having a coating layer without using the available chlorine content or the available oxygen content, a calculation method based on the following Formula 6 can be employed.

[0143] Proportion of coating layer (mass%) = Q1 x 100 / Q2 (Formula 6)

[0144] Q1: Mass (g) of the coating layer in the solid bleaching agent-containing article having a coating layer

[0145] Q1: mass (g) of the coating layer in the solid bleaching agent containing object with the coating layer

[0146] For example, in the case where 0.3 g of the coating layer is contained in the solid bleaching agent containing object with the coating layer 1 g, the proportion (mass %) of the coating layer is 0.3 x 100 / 1 = 30 according to Formula 6, and reaches 30%.

[0147] The identification and quantification of the coating layer can be determined by known methods. For example, in the case where the absorbance of the compound used in the coating layer is known, the content of the coating layer can be calculated using the absorbance adjusted to the known concentration of the compound for the coating layer to make a calibration curve, or known methods such as liquid chromatography, gas chromatography, and the like can be used for the determination. In the case where the quantification of the solid bleaching agent is easier than the quantification of the coating layer, the mass of the coating layer can be calculated from the mass of the solid bleaching agent according to the following Formula 7.

[0148] Mass Q1 of the coating layer = Q2 - Q3 (Formula 7)

[0149] Q1: mass (g) of the coating layer in the solid bleaching agent containing object with the coating layer

[0150] Q2: mass (g) of the solid bleaching agent containing object with the coating layer

[0151] Q3: mass (g) of the solid bleaching agent in the solid bleaching agent containing object with the coating layer

[0152] The processing device used in the production of the solid bleaching agent containing object of the present application is not particularly limited, and one or more processing devices selected from the group of commercially available mixers, tumblers, fluidized bed machines, and devices combining them can be used. The processing can be completed with one processing device, or a plurality of processes can be performed with different processing devices. From the viewpoint of ease of processing, one or more processing devices selected from the group of tumblers, fluidized bed machines, and devices combining them are preferred.

[0153] As the processing device, there can be mentioned devices sold under the trade names of, specifically, DPZ-01 (manufactured by Asahi Process Co., Ltd.), Swirl Fluidized Bed (manufactured by Dalton Co., Ltd.), New-Gra Machine (manufactured by Seishin Enterprise Co., Ltd.), Swirler (registered trademark) (manufactured by Japan Pneumatic Industries, Inc.), Loedige mixer (manufactured by Matsubo Co., Ltd.), Granurex (registered trademark) (manufactured by Freund Industry Co., Ltd.), Spir-A-Flow (registered trademark) (manufactured by Freund Industry Co., Ltd.), CF granulator (manufactured by Freund Industry Co., Ltd.), High Speed Mixer (manufactured by Earth Technica Co., Ltd.), High Speed Vacuum Dryer (manufactured by Earth Technica Co., Ltd.), Dynamic Dryer (manufactured by Earth Technica Co., Ltd.), Multiplex (manufactured by Powrex Co., Ltd.), Vertical Granulator (manufactured by Powrex Co., Ltd.), Agromaster (registered trademark) (manufactured by Hosokawa Micron Co., Ltd.), Nara Mixer & Granulator (manufactured by Nara Machinery Mfg. Co., Ltd.), and the like. As the processing device which can be preferably used, there can be mentioned DPZ-01, Swirl Fluidized Bed, New-Gra Machine, Granurex, Spir-A-Flow, CF granulator, High Speed Mixer, High Speed Vacuum Dryer, Dynamic Dryer, Multiplex, Vertical Granulator.

[0154] In the production of the solid bleaching agent-containing article of the present application, a process of keeping the solid bleaching agent to be a raw material in a fluidized state and a process of bringing the solid bleaching agent in the fluidized state into contact with a coating liquid are included. The fluidized state of the solid bleaching agent can be performed by stirring, rotation, or the like, or by an air stream supplied from a blower or the like. The fluidized state of the solid bleaching agent at this time is preferably set so as not to destroy the strength of the solid bleaching agent.

[0155] The strength of the fluidized state can be determined as follows: in the case where the solid bleaching agent for processing is made into a fluidized state by the processing device or other method and is fluidized for the time required to form the coating layer, the strength of the fluidized state is determined by measuring the change in the average particle diameter of the solid bleaching agent. That is, the smaller the average particle diameter of the solid bleaching agent after the solid bleaching agent is treated in a fluidized state for a predetermined time compared to the average particle diameter before fluidization, the stronger the strength of the fluidized state, and thus the solid bleaching agent is destroyed. For example, in the case of a blender, the strength of the fluidized state is adjusted by the rotational speed during stirring. It is considered that the faster the rotational speed during stirring, the stronger the strength of the fluidized state. For example, in the case of a fluidized bed device, in order to make the raw material into a fluidized state, the strength of the fluidized state can be adjusted by the air volume or air speed of the supplied air (hereinafter, referred to as fluidizing air). It is considered that the greater the air volume or the faster the air speed, the stronger the strength of the fluidized state.

[0156] In the case where the strength of the fluidized state is too strong, the coating layer and the solid bleaching agent or either of them are destroyed and micronized at the same time as the coating layer of the solid bleaching agent is formed, and thus the coating layer is not formed on the solid bleaching agent or is formed to be insufficient. In this case, it is preferable to reduce the strength of the fluidized state. The strength of the fluidized state can be reduced by reducing the rotational speed of the blender, the rotational speed of the rotating machine, or the flow rate of the fluidizing air of the fluidized bed device. Thus, for example, in the case where the solid bleaching agent is a powder or a granule, in the case where the average particle diameter of the solid bleaching agent after the solid bleaching agent is treated in a fluidized state for a predetermined time is too small compared to the average particle diameter before the treatment, the strength of the fluidized state is too strong, and thus it is preferable to reduce the strength of the fluidized state by reducing the rotational speed or the air flow rate. However, the average particle diameter of the solid bleaching agent or the solid bleaching agent-containing substance after the treatment can be smaller than the average particle diameter of the solid bleaching agent before the treatment, within a range that does not impair the effects of the present application.

[0157] On the other hand, in a case where the intensity of the fluidized state is too weak, the solid bleaching agent is not sufficiently fluidized, and thus the formation of the coating layer becomes insufficient, and aggregation of the solid bleaching agent, adhesion to the inner wall of the device, and the like are caused. In the process of forming the coating layer on the solid bleaching agent, as the coating layer increases, the average particle diameter of the solid bleaching agent-containing material generally becomes larger than the average particle diameter of the solid bleaching agent before processing, but in a case where aggregation of the particles with each other is caused, the average particle diameter of the solid bleaching agent-containing material sometimes sharply increases. In a case where the average particle diameter of the solid bleaching agent-containing material after processing is extremely large, it is indicated that the aggregation of the solid bleaching agent sharply proceeds at the time of processing. The large particles resulting from the aggregation cause, for example, poor dispersion of the solid bleaching agent when incorporated into a detergent composition, and the like, and thus are not preferable. Thus, in a case where the intensity of the fluidized state is too weak, it is preferable to increase the intensity of the fluidized state by increasing the rotation speed of the agitator, the rotation machine, the flow rate of the fluidizing air of the fluidized bed device. However, within a range not impairing the effects of the present application, it is allowed that the average particle diameter of the solid bleaching agent or the solid bleaching agent-containing material after processing is larger than the average particle diameter of the solid bleaching agent before processing. Thus, the intensity of the fluidized state can be appropriately set.

[0158] In addition, at the time of adding or spraying the coating liquid, in a case where the supply speed of the coating liquid is too fast, the solid bleaching agent is excessively wetted without being limited by the intensity of the fluidized state, and thus aggregation of the solid bleaching agent, adhesion to the inner wall of the device, and the like are caused. In such a case, it is preferable to decrease the supply speed of the coating liquid. On the other hand, in a case where the supply speed of the coating liquid is too slow, the process takes too much time, and thus it is preferable to increase the supply speed of the coating liquid within a range not causing aggregation or adhesion of the solid bleaching agent. Thus, the supply speed of the coating liquid can be appropriately set. In addition, depending on the kind of the compound used for the coating layer, the degree of aggregation also differs, and thus it is preferable to select a compound which is not easily aggregated as the coating layer. As described above, by appropriately adjusting the intensity of the fluidized state of the solid bleaching agent and the supply speed of the coating liquid within a range not impairing the solid bleaching agent and not causing aggregation or adhesion, the solid bleaching agent-containing material having a coating layer of the present application can be manufactured.

[0159] In order to evaluate to what extent the micronization, aggregation occurs at the time of processing the solid bleaching agent-containing material having a coating layer, the reduction rate or the increase rate of the average particle diameter of the solid bleaching agent-containing material having a coating layer after processing with respect to the average particle diameter of the solid bleaching agent used as a raw material is defined as an aggregation rate according to the following Formula 8.

[0160] Aggregation rate (%) = D1 x 100 / D2 (Formula 8)

[0161] D1: Average particle diameter of the solid bleaching agent-containing material having a coating layer after processing

[0162] D2: Average particle diameter of the solid bleaching agent for raw material

[0163] The aggregation rate is preferably 80% or more and 300% or less, more preferably 85% or more and 250% or less, and further preferably 90% or more and 200% or less. In the case where the aggregation rate is 80% or more, the coating layer of the solid bleaching agent is formed at the time of processing, and on the other hand, the micronization of either or both of the coating layer and the solid bleaching agent is within an allowable range, and thus it is preferred that, in the case where it is 85% or more, the degree of micronization is smaller, and thus it is more preferred that, in the case where it is 90% or more, the degree of micronization is further smaller, and thus it is further preferred. On the other hand, in the case where the aggregation rate is 300% or less, the aggregation of the particles at the time of processing is within an allowable range, and thus in the case where it is combined with a detergent composition or the like, the operation is easy, and thus it is preferred that, in the case where it is 250% or less, the operation is easier, and thus it is more preferred that, in the case where it is 200% or less, the operation is further easy, and thus it is further preferred.

[0164] The stability of the solid bleaching agent content having a coating layer thus obtained is evaluated in terms of how much the effective chlorine retention or the effective oxygen retention is improved before and after coating under a certain condition after a storage test. The effective chlorine retention (%) is defined according to the following Formula 9. The closer the effective chlorine retention (%) is to 100%, the more stable the solid bleaching agent is, and the closer it is to 0%, the less stable the solid bleaching agent is. Also, in the case where the solid bleaching agent is an oxygen-containing bleaching agent, the stability of the solid bleaching agent is defined by the effective oxygen retention (%). In the case where the solid bleaching agent content having a coating layer and the solid bleaching agent not having a coating layer are respectively subjected to a storage test under the same condition, in the case where the solid bleaching agent content having a coating layer shows a higher effective chlorine retention or effective oxygen retention than the solid bleaching agent not having a coating layer, it can be said that the stability of the solid bleaching agent is improved.

[0165] Effective chlorine or effective oxygen retention (%) = R1 x 100 / R2 (Formula 9)

[0166] R1: Effective chlorine or effective oxygen content (%) of the solid bleaching agent or the solid bleaching agent content after a storage test

[0167] R2: Effective chlorine or effective oxygen content (%) of the solid bleaching agent or the solid bleaching agent content before a storage test

[0168] The following method can be employed as a condition for a storage test for evaluating the stability of the solid bleaching agent.

[0169] For example, when the solid bleaching agent containing body with the coating layer of the present application and the bleaching agent without the coating layer are stored for a certain period of time in an environment where factors deteriorating, deactivating, decomposing the solid bleaching agent exist, there is a difference in stability of the solid bleaching agent. At this time, the factors deteriorating, deactivating, decomposing the solid bleaching agent are not particularly limited, and examples thereof include acidity, alkalinity, high temperature, high humidity, etc.

[0170] When the storage test is performed, the solid bleaching agent can be mixed with other compounds. As the other compounds, one or more selected from the group of the organic substance, the inorganic substance, and a mixture thereof can be used. For example, the storage test can be performed by storing only the solid bleaching agent containing body with the coating layer under high temperature and high humidity for a certain period of time, or by storing the solid bleaching agent containing body with the coating layer in combination with a cleaning agent composition for a certain period of time. In addition, the storage test can be performed after the solid bleaching agent containing body with the coating layer is previously subjected to physical impact or after the solid bleaching agent containing body with the coating layer is subjected to a stirring, mixing, or the like process together with the cleaning agent composition.

[0171] In addition, the temperature, humidity, and packaging form at the time of storage in the storage test can be appropriately changed. For example, it can be performed under normal temperature and pressure conditions, or the temperature and humidity can be controlled to be performed under an environment of, for example, a temperature of 40°C and a relative humidity of 75%. In addition, the solid bleaching agent containing body for the test can be used directly, or can be used by being put into a film or a container.

[0172] After the storage test under such conditions is completed, when the solid bleaching agent containing body with the coating layer shows a higher effective chlorine retention rate or effective oxygen retention rate than the solid bleaching agent without the coating layer, it can be said that the stability of the solid bleaching agent is improved. The higher the effective chlorine retention rate or effective oxygen retention rate, the more the cleaning, sterilization, bleaching effects of the solid bleaching agent after storage are maintained. The extent to which the stability of the solid bleaching agent is improved varies not only depending on the properties of the solid bleaching agent containing body with the coating layer, but also depending on the condition setting of the storage test. Depending on the purpose and use conditions of the solid bleaching agent, the condition setting of the storage test can be set in a range other than those described in the present specification. It is preferable that the stability of the solid bleaching agent is improved to a degree suitable for the purpose and use conditions regardless of the storage test.

[0173] Examples

[0174] Hereinafter, the present application will be specifically described by examples and comparative examples, but the present application is not limited thereto.

[0175] Hereinafter, the main chemical reagents used in the experiments are described.

[0176] • Sodium benzoate, sodium p-t-butylbenzoate, o-phthalic acid, m-phthalic acid, p-phthalic acid, trimellitic acid: manufactured by Wako Pure Chemical Industries, Ltd. (reagent)

[0177] • Disodium o-phthalate, disodium m-phthalate, disodium p-phthalate, trisodium trimellitate: each of o-phthalic acid, m-phthalic acid, p-phthalic acid, trimellitic acid was dissolved in an aqueous sodium hydroxide solution to prepare.

[0178] • Sodium formate, sodium acetate, sodium propionate, sodium butyrate, valeric acid, caproic acid, heptanoic acid, caprylic acid, capric acid: manufactured by Wako Pure Chemical Industries, Ltd. (reagent)

[0179] • Sodium valerate, sodium caproate, sodium heptanoate, sodium caprylate: each of valeric acid, caproic acid, heptanoic acid, caprylic acid, capric acid was dissolved in an aqueous sodium hydroxide solution to prepare.

[0180] • Succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid: manufactured by Wako Pure Chemical Industries, Ltd. (reagent)

[0181] • Glutaric acid, pimelic acid, suberic acid, myristic acid: manufactured by Tokyo Chemical Industry Co., Ltd. (reagent)

[0182] • Disodium succinate, disodium glutarate, disodium adipate, disodium pimelate, disodium suberate, disodium sebacate, disodium dodecanedioate, disodium myristate: each of succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, dodecanedioic acid, myristic acid was dissolved in an aqueous sodium hydroxide solution to prepare.

[0183] • Sodium hydroxide: manufactured by Wako Pure Chemical Industries, Ltd. (reagent)

[0184] • Myristic acid: manufactured by Wako Pure Chemical Industries, Ltd. (reagent)

[0185] • Sodium alkylbenzenesulfonate: manufactured by Lion Corporation "Lipon (registered trademark) PS-230"

[0186] • Sodium lauryl sulfate: manufactured by Kawabata Kagaku K.K. "Emal (registered trademark) 10PT"

[0187] • Silicone-based defoaming agent: manufactured by Shin-Etsu Chemical Co., Ltd. "KM-89"

[0188] • Sodium α-olefin sulfonate: manufactured by Lion Corporation "Lipolan (registered trademark) PB-800"

[0189] • Hydroxypropyl cellulose: manufactured by Wako Pure Chemical Industries, Ltd. (reagent)

[0190] • Sodium caprylate, sodium laurate: manufactured by Wako Pure Chemical Industries, Ltd. (reagent)

[0191] • Sodium bicarbonate, sodium sulfate: manufactured by Wako Pure Chemical Industries, Ltd. (reagent)

[0192] • Paraffin (melting point 58-60°C): manufactured by Wako Pure Chemical Industries, Ltd. (reagent)

[0193] • Stearyl alcohol: manufactured by Wako Pure Chemical Industries, Ltd. (reagent)

[0194] • Fine zeolite (synthetic zeolite A-4, average particle diameter 2-5 μm): manufactured by Wako Pure Chemical Industries, Ltd. (reagent)

[0195] • Sodium dichloroisocyanurate: manufactured by Shikoku Chemicals Corporation "Neo-Chlor (registered trademark) 60G" (average particle diameter 700 μm)

[0196] • Trichloroisocyanuric acid: manufactured by Shikoku Chemicals Corporation "Neo-Chlor 90G" (average particle diameter 1097 μm)

[0197] • Sodium percarbonate (sodium carbonate hydrogen peroxide adduct): manufactured by Adeka Corporation "PC-2" (average particle diameter 746 μm)

[0198] • Oxone (registered trademark) (average particle diameter 516 μm)

[0199] • Mixture of bromochloro-5,5-dimethylhydantoin, 1,3-dichloro-5,5-dimethylhydantoin, 1,3-dichloro-5,5-ethylmethylhydantoin (hereinafter referred to as halogenated hydantoin mixture): manufactured by Lonza Japan Corporation "DANTOBROM RW" (average particle diameter 886 μm)

[0200] • Sodium metasilicate: manufactured by Sigma-Aldrich Corporation (reagent)

[0201] • Sodium metasilicate pentahydrate: manufactured by Sigma-Aldrich Corporation (reagent)

[0202] • Sodium metasilicate nonahydrate: manufactured by Sigma-Aldrich Corporation (reagent)

[0203] • Trisodium nitrilotriacetate monohydrate: manufactured by Wako Pure Chemical Industries, Ltd. (reagent)

[0204] • Potassium carbonate: manufactured by Wako Pure Chemical Industries, Ltd. (reagent)

[0205] • Potassium sulfate: manufactured by Wako Pure Chemical Industries, Ltd. (reagent)

[0206] • Sodium oleate-maleic anhydride copolymer: "ACUSOL (registered trademark) 460ND" manufactured by Rohm & Haas

[0207] • Ethylenediamine-polyoxyethylene-polyoxypropylene block polymer: "Adeka Pluronic TR-702" manufactured by Adeka Corporation

[0208] • Ethanol: "Reagent Extra Pure" manufactured by Wako Pure Chemical Industries, Ltd.

[0209] • Other reagents and instruments: General products available on the market were used.

[0210] (Example 1)

[0211] Sodium dichloroisocyanurate was used as the solid bleaching agent. 100 g of sodium dichloroisocyanurate was put into a processing device "DPZ-01" (manufactured by Asahi Seiki Co., Ltd.), the rotation speed of the rotating disk was set to 40 rpm, the elevation angle was set to 45°, and the heater temperature was set to Hi, while the sodium dichloroisocyanurate was kept in a fluidized state with heating. Note that the elevation angle refers to the angle formed by the direction of the rotation axis of the rotating disk and the horizontal direction. At this time, the faster the rotation speed and the smaller the elevation angle, the more vigorously the sodium dichloroisocyanurate in the fluidized state moves, and thus the stronger the strength of the fluidized state can be said to be. The rotation speed, the elevation angle, and the heater temperature can be appropriately adjusted within a range in which the fluidization of the solid bleaching agent can be maintained. That is, it should be adjusted so that the coating liquid in which the solid bleaching agent is sprayed is more uniformly wetted. For example, in the case where the solid bleaching agent is retained below the rotating disk and the fluidization is insufficient, by increasing the rotation speed or increasing the elevation angle, the solid bleaching agent is easily spread over the entire rotating disk. On the other hand, in the case where the rotation speed of the rotating disk is too fast or the elevation angle is too large, the solid bleaching agent is retained in the circumferential direction due to the centrifugal force of the rotating disk and the fluidization becomes insufficient, and thus by slowing down the rotation speed or reducing the elevation angle, the solid bleaching agent can be fluidized again to be spread over the entire rotating disk.

[0212] The fluidized sodium dichloroisocyanurate was sprayed with 25 mass% sodium benzoate aqueous solution (coating liquid) to wet the sodium dichloroisocyanurate. At this time, the coating liquid was supplied at a liquid rate of about 1 g / min using a tube pump at a spraying speed of about 1 g / min. To supply the coating liquid, a silicone tube having an inner diameter of 2 mm was used. During spraying, 0.1 MPa of compressed air was introduced into the atomizer nozzle using a polyethylene tube having an inner diameter of 2 mm. A two-fluid nozzle (model AM25, manufactured by Atomax Corporation) was used as the atomizer nozzle, and 0.1 MPa of compressed air was supplied to atomize the coating liquid. Since the rotating disk had been heated, the water in the coating liquid that wetted the sodium dichloroisocyanurate was dried and removed, and a coating layer formed of sodium benzoate slowly formed on the surface of the sodium dichloroisocyanurate. The operation was completed when 342 g of the coating liquid was sprayed, and a sample 176 g of a solid bleaching agent-containing product containing sodium benzoate in the coating layer was obtained. The processing conditions can be appropriately changed when the types and amounts of the compounds used for the solid bleaching agent and the coating layer are changed.

[0213] Water content

[0214] The total amount of the prepared sample was dried in an oven set to 110°C, and as a result, a constant amount was reached in 1.5 hours, and the weight at that time was 163 g. The amount of water remaining in the sample immediately after processing (hereinafter, sometimes referred to as "water content") was thus calculated to be 7.4 mass% as described in Table 1. The yield based on the weight of the solid bleaching agent and the coating material used was 88% based on the weight after drying.

[0215] Proportion of available chlorine content to coating layer

[0216] The dried sample was weighed in the range of 0.10 g to 0.13 g, and the mass was accurately recorded to four decimal places, and was placed in a 200-ml conical beaker, distilled water was added to adjust to about 100 ml, about 1 g of potassium iodide and about 5 ml of 50 mass% acetic acid aqueous solution were added, and stirring was performed for about 5 minutes. The free iodine was titrated with 0.1 N sodium thiosulfate aqueous solution, and after the yellow color of the solution faded, about 1 ml of starch aqueous solution (10 g / L) as an indicator was added, and the titration was continued until the blue color of the generated iodine starch disappeared, and the available chlorine content (%) was calculated from the amount of sodium thiosulfate aqueous solution titrated. As a result, the available chlorine content of the dried sample was 38.0%. At this time, the available chlorine content of the sodium dichloroisocyanurate used as a raw material was 62.5%, which was slightly lower than the theoretical value, and thus the proportion of the coating layer in the dried sample was calculated to be 39 mass% as described in Table 1. It is considered that the dried sample had a coating layer containing sodium benzoate, and was a solid bleaching agent-containing product in which the coating layer accounted for 39 mass% of the total weight. The processing conditions can be appropriately changed when the types and amounts of the compounds used for the solid bleaching agent and the coating layer are changed.

[0217] (Example 2)

[0218] 500 g of sodium dichloroisocyanurate was used as a solid bleaching agent. The sodium dichloroisocyanurate was put into a processing device "Spir-A-Flow" (Model SFC-MINI, manufactured by Freund Industrial Co., Ltd.). The opening degree of the exhaust air damper was set to 7.5, the opening degree of the fluidizing air damper was set to 6, the opening degree of the slit air damper was set to 7, and the temperature of the air supply heater was set to 100°C. The rotational speed of the rotor was set to 300 rpm, and the device was started to make the sodium dichloroisocyanurate into a fluidized state. At this time, the greater the opening degree of each damper of the exhaust air, fluidizing air, and slit air and the faster the rotational speed of the rotor, the more vigorously the sodium dichloroisocyanurate moves, and thus the strength of the fluidized state can be said to be strong.

[0219] At the time when the temperature of the sodium dichloroisocyanurate in the fluidized state reached 60°C, a 36 mass% sodium benzoate aqueous solution (coating liquid) was sprayed at a flow rate of about 20 g / min in the spraying speed. At the time of spraying the coating liquid, 0.1 MPa of compressed air was supplied at a flow rate of 20 L / min. The temperature of the sodium dichloroisocyanurate was measured by a thermometer provided in the layer and displayed as the product temperature. The supply speed of the coating liquid was finely adjusted so that the product temperature became in the range of 60°C ± 10°C. A two-fluid nozzle (Model ATU-MINI, manufactured by Freund Industrial Co., Ltd.) was used as the sprayer nozzle. The processing was ended at the time when 540 g of the coating liquid was sprayed, and a sample 692 g of the solid bleaching agent-containing product was obtained. The processed sample was taken out from the device, and became constant in amount at the time when dried in a drier at 110°C for 1.5 hours. The processing conditions can be appropriately changed in the case of changing the kind and amount of the compound used for the solid bleaching agent and the coating layer.

[0220] The water content, the available chlorine content, the yield, and the proportion of the coating layer were calculated in the same manner as in Example 1 (the same applies hereinafter). As a result, the water content was 1.9 mass%, the available chlorine content was 46.3%, and the proportion of the coating layer was 26 mass% as described in Table 1.

[0221] Stability Test 1 (Storage Test)

[0222] A storage test was performed using sodium dichloroisocyanurate as a solid bleaching agent without processing and the samples produced in Example 1 and Example 2 and dried at 110°C for 1.5 hours as solid bleaching agent-containing objects with coating layers. Anhydrous sodium metasilicate 3 g, potassium carbonate 2.0 g, trisodium nitrilotriacetate monohydrate 4.75 g, ethylenediamine-polyoxyethylene-polyoxypropylene block polymer 0.1 g, solid bleaching agent or solid bleaching agent-containing object 0.15 g were mixed, put in a glass beaker of 50 ml capacity, 3 ml of tap water at 60°C was added, and the mixture was gently stirred in a circular manner with a spatula. At this time, the room temperature was 20°C and the relative humidity was 40%. The mixture was left to stand at room temperature for 18 hours, and then the entire mixture was dissolved in 200 ml of distilled water, the available chlorine content was measured, and the available chlorine retention rate was calculated. The available chlorine retention rate after coating (available chlorine retention rate after coating) when using the solid bleaching agent-containing object with a coating layer was improved compared to the available chlorine retention rate before coating (available chlorine retention rate before coating) when using the solid bleaching agent without processing, and in this case, the stability of the solid bleaching agent was improved, so it was evaluated as O as a pass, and in the case where there was no improvement, or in the case of a decrease, the stability of the solid bleaching agent could not be said to be improved, so it was evaluated as X as a fail. The available chlorine retention rates of sodium dichloroisocyanurate before coating and the samples produced in Example 1 and Example 2 after the storage test are shown in Table 10.

[0223] Foaming test (foaming evaluation)

[0224] A water solution was produced by dissolving the solid bleaching agent-containing object with a coating layer produced in Example 1 and Example 2 and dried at 110°C for 1.5 hours in water to a concentration of 0.2 mass%, and 20 ml of the water solution was put in a 100 ml capacity cuvette. The cuvette was left to stand in a constant temperature water bath at 60°C for 30 minutes, and then the cuvette was vigorously shaken up and down 10 times with both hands while holding the lid of the cuvette. The amount of foam immediately after shaking was read from the scale of the cuvette, and the foaming amount was evaluated. For the evaluation results of the foaming amount, cases where no foaming occurred or the foam was less than 1 ml were recorded as O as a pass, cases where foam was generated and the foam was 1 ml or more and less than 30 ml under the scale of the cuvette were recorded as X as a fail since foam was generated, and cases of 30 ml or more were recorded as XX as a fail since the foam was excessively large. The results are shown in Table 10. Note that the capacity of the cuvette was 100 ml, and thus the measurable amount of foam was up to 80 ml. Therefore, the amount of foam when the foaming amount was greater than 80 ml was recorded as "80 <".

[0225] Solubility test (residue evaluation)

[0226] The solid bleaching agent-containing article was dissolved in 100 ml of water at 40°C to form a concentration of 0.2 mass% and 5 mass%, respectively, and the undissolved residue was evaluated by visual observation. In the presence of undissolved residue, stirring was continued for 30 minutes or more, and then the evaluation was performed. The absence of residue from the undissolved coated layer on the water surface and at the water bottom at any concentration was evaluated as O, the presence of residue from the undissolved coated layer on the water surface and at the water bottom at a concentration of 5 mass% but the absence of residue from the undissolved coated layer on the water surface and at the water bottom at a concentration of 0.2 mass% was evaluated as X, and the presence of residue from the undissolved coated layer on the water surface and at the water bottom at any concentration was evaluated as XX. The results are shown in Table 10.

[0227] (Examples 3 to 7)

[0228] In addition to the conditions described in Table 1, a sample of a solid bleaching agent-containing article having a coated layer was produced using sodium p-t-butylbenzoate, disodium o-phthalate, disodium m-phthalate, disodium p-phthalate, trisodium trimellitate in the same manner as in Example 2. The concentration (mass%) of the coating solution, the water content (mass%) of the produced sample, and the proportion of the coated layer (mass%) are shown in Table 1. For each sample, the stability test 1, the foaming test, and the solubility test were performed using the sample dried at 110°C for 1.5 hours in the same manner as in the case of Example 1 and Example 2. The results are shown in Table 10.

[0229] (Examples 8 to 16)

[0230] In addition to the conditions described in Table 2, a sample of a solid bleaching agent-containing article having a coated layer was produced using disodium succinate, disodium glutarate, disodium adipate, disodium pimelate, disodium suberate, disodium azelate, disodium sebacate, disodium dodecanedioate, and disodium tetradecanedioate in the same manner as in Example 1 or Example 2. The concentration (mass%) of the coating solution, the water content (mass%) of the produced sample, and the proportion of the coated layer (mass%) are shown in Table 2. For each sample, the stability test 1, the foaming test, and the solubility test were performed using the sample dried at 110°C for 1.5 hours in the same manner as in the case of Example 1 and Example 2. The results are shown in Table 11.

[0231] (Examples 17 to 23)

[0232] In addition to the conditions described in Table 3, samples of the solid bleaching agent-containing article having a coating layer were produced using sodium formate, sodium acetate, sodium propionate, sodium butyrate, sodium valerate, sodium hexanoate, and sodium heptanoate as the coating liquid in the same manner as in Example 1 or Example 2. The concentration of the coating liquid (mass %), the water content of the produced sample (mass %), and the proportion of the coating layer (mass %) are shown in Table 3. For each sample, the stability test 1, the foaming test, and the solubility test were performed using the sample dried at 110°C for 1.5 hours in the same manner as in the case of Example 1 and Example 2. The results are shown in Table 12.

[0233] (Examples 24 to 29)

[0234] In addition to the conditions described in Table 4, samples of the solid bleaching agent-containing article having a coating layer were produced using two compounds in the same manner as in Example 2 so that the coating layer further contained two layers. That is, as a first step, a solid bleaching agent-containing article having a coating layer was produced using sodium benzoate as the coating liquid, and as a second step, the solid bleaching agent-containing article having a coating layer produced in the first step was further used to form a coating layer using disodium sebacate or disodium dodecanedioate, thereby producing samples of the solid bleaching agent-containing article having a coating layer with an inner layer containing sodium benzoate and an outer layer containing disodium sebacate or disodium dodecanedioate. The concentration of the coating liquid (mass %), the water content of the produced sample (mass %), and the proportion of the coating layer (mass %) are shown in Table 4. For each sample, the stability test 1, the foaming test, and the solubility test were performed using the sample dried at 110°C for 1.5 hours in the same manner as in the case of Example 1 and Example 2. The results are shown in Table 13. Note that the proportion of the coating layer was quantified using high-performance liquid chromatography (HPLC) for Examples 24 to 29. Hereinafter, the quantification method is described in detail.

[0235] As the device, a high performance liquid chromatograph LC-2010AHT (manufactured by Shimadzu Corporation) was used. As the column, a high performance liquid chromatograph column HITACHI LaChrom (registered trademark) C18-AQ (manufactured by Hitachi High-Tech Science Corporation) was used. As the mobile phase, a solvent in which a 60 mM aqueous diammonium hydrogen phosphate solution and methanol were mixed so that the weight ratio became 9: 1 was used. The flow rate of the mobile phase was set to 1 ml / min, and the temperature of the column oven was set to 40°C. In the detection, ultraviolet rays of wavelength 210 nm were used. Under the conditions thus set, a calibration curve of the peak area versus the concentration was prepared using an aqueous solution of sodium dichloroisocyanurate in which the available chlorine was neutralized with an equivalent amount of sodium sulfite, an aqueous sodium benzoate solution, and an aqueous disodium sebacate solution, each of which had a known concentration. At this time, the peak from sodium dichloroisocyanurate was detected at a retention time of about 3.0 minutes, the peak from sodium benzoate was detected at a retention time of about 8.0 minutes, and the peak from disodium sebacate was detected at a retention time of about 11.5 minutes.

[0236] Under the same conditions as the HPLC, the samples prepared in Examples 24 to 29, each of which had a known concentration, were measured, and sodium dichloroisocyanurate, sodium benzoate, and sodium sebacate were quantified, respectively, and the proportion of the coating layer (mass %) was calculated according to Formula 6. Note that, for the samples prepared in Examples 27 to 29, which contained disodium dodecanedioate, only sodium dichloroisocyanurate and sodium benzoate were quantified, and in Formula 7, Q2 was taken as the total amount, Q3 was taken as the total amount of sodium dichloroisocyanurate and sodium benzoate, and the remaining Q1 was taken as disodium dodecanedioate, as the content of each component.

[0237] (Examples 30 to 35)

[0238] In addition to the conditions described in Table 5, samples of the solid bleaching agent containing body having a coating layer containing a mixture of two compounds were prepared in the same manner as in Example 2. That is, using a mixed solution containing sodium benzoate as a first component and disodium sebacate or disodium dodecanedioate as a second component as a coating liquid, a solid bleaching agent containing body having a coating layer containing a mixture of sodium benzoate and disodium sebacate or sodium benzoate and disodium dodecanedioate was prepared. The concentration (mass %) of the coating liquid, the water content (mass %) of the prepared sample, and the proportion of the coating layer (mass %) are shown in Table 5. The proportion of the coating layer was quantified using HPLC in the same manner as in the case of Examples 24 to 29. For each sample, the sample after drying at 110°C for 1.5 hours was used to perform the stability test 1, the foaming test, and the solubility test in the same manner as in the case of Examples 1 and 2. The results are shown in Table 14.

[0239] (Examples 36 to 37)

[0240] In addition to the conditions described in Table 6, samples of solid bleaching agent-containing articles having a coating layer were produced using two compounds in the same manner as in Examples 24 to 29, so that the coating layer further contained two layers. That is, as a first step, a solid bleaching agent-containing article having a coating layer was produced using sodium benzoate for the coating layer, and as a second step, sodium caprylate or sodium caprate was further used for the solid bleaching agent-containing article having a coating layer produced in the first step to further form a coating layer, thereby producing samples of solid bleaching agent-containing articles having a coating layer further having an inner layer containing sodium benzoate and an outer layer containing sodium caprylate or sodium caprate. The concentration of the coating solution (mass %), the water content of the produced samples (mass %), and the proportion of the coating layer (mass %) are shown in Table 6. The proportion of the coating layer was quantified by HPLC in the same manner as in the case of Examples 24 to 29. For each sample, the stability test 1, the foaming test, and the solubility test were performed in the same manner as in the case of Examples 1 and 2 using the sample dried at 110°C for 1.5 hours. The results are shown in Table 15.

[0241] Thus, a compound other than 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 dibasic carboxylic acid, an alkali metal salt of an acyclic monobasic carboxylic acid having 1 to 7 carbon atoms, and a mixture thereof can also be included in the coating layer without impairing the effects of the present application.

[0242] (Examples 38 to 39)

[0243] In addition to the conditions described in Table 7, samples of solid bleaching agent-containing articles having a coating layer were produced in the same manner as in Examples 30 to 35, the coating layer containing a mixture of two compounds. That is, a solid bleaching agent-containing article having a coating layer was produced using a mixed solution of sodium benzoate and sodium caprylate or a mixed solution of sodium benzoate and sodium caprate as a coating solution, the coating layer containing a mixture of sodium benzoate and sodium caprylate or a mixture of sodium benzoate and sodium caprate. The concentration of the coating solution (mass %), the water content of the produced samples (mass %), and the proportion of the coating layer (mass %) are shown in Table 7. The proportion of the coating layer was quantified by HPLC in the same manner as in the case of Examples 24 to 29. For each sample, the stability test 1, the foaming test, and the solubility test were performed in the same manner as in the case of Examples 1 and 2 using the sample dried at 110°C for 1.5 hours. The results are shown in Table 16.

[0244] (Comparative Examples 1 to 8)

[0245] A sample of a solid bleaching agent-containing substance having a coating layer was produced using sodium lauryl sulfate, sodium alkylbenzenesulfonate, sodium alpha-olefin sulfonate, hydroxypropyl cellulose, sodium laurate, sodium octanoate, sodium bicarbonate, and sodium sulfate for the coating layer, in the same manner as in Example 1 or Example 2, except for the conditions described in Table 8. In the case where the spraying speed during production was too fast, there were cases where the particles aggregated with each other or the solid bleaching agent adhered to the inner wall of the apparatus. In such cases, the aggregation and adhesion could be avoided by making the supply speed of the coating liquid slower. The aggregated and adhered particles could be dispersed without damaging the particles using a soft tool such as a rubber spatula. The concentration (mass %) of the coating liquid, the water content (mass %) of the produced sample, and the proportion (mass %) of the coating layer are shown in Table 8. For each sample, the sample after drying at 110°C for 1.5 hours was used to perform the stability test 1, the foaming test, and the solubility test, in the same manner as in the case of Example 1 and Example 2. The results are shown in Table 17.

[0246] (Comparative Example 9)

[0247] A sample of a solid bleaching agent-containing substance having a coating layer was produced using myristic acid for the coating layer, in the same manner as in Example 1, except for the point that the fluidized sodium dichloroisocyanurate was sprayed with an ethanol solution of myristic acid adjusted to a concentration of 22 mass % to thereby wet the sodium dichloroisocyanurate and the conditions described in Table 9. The concentration (mass %) of the coating liquid and the proportion (mass %) of the coating layer are shown in Table 9. No water was used as the solvent, and therefore no drying step was provided, and the water content was not measured. For the sample produced in Comparative Example 9, the stability test 1, the foaming test, and the solubility test were performed in the same manner as in the case of Example 1 and Example 2. The results are shown in Table 18.

[0248] (Comparative Example 10)

[0249] A coating liquid was produced by dissolving sodium lauryl sulfate to 24 mass % and dispersing a polysiloxane-based defoaming agent (KM-89) to 5 mass %. A sample of a solid bleaching agent-containing substance having a coating layer in which the coating layer contained a mixture of sodium lauryl sulfate and the polysiloxane-based defoaming agent was produced in the same manner as in Example 1, except for the point that the coating liquid was sprayed to thereby wet the sodium dichloroisocyanurate and the conditions described in Table 9. The concentration (mass %) of the coating liquid, the water content (mass %) of the produced sample, and the proportion (mass %) of the coating layer are shown in Table 9. For the sample produced in Comparative Example 10, the sample after drying at 110°C for 1.5 hours was used to perform the stability test 1, the foaming test, and the solubility test, in the same manner as in the case of Example 1 and Example 2. The results are shown in Table 18.

[0250] (Comparative Example 11)

[0251] Into a processing device "DPZ-01" (manufactured by YASUWA Co., Ltd.), 70 g of sodium dichloroisocyanurate was put, the rotation speed of the rotating disk was set to 40 rpm, the elevation angle was set to 45°, and the heater temperature was set to Hi, while heating, the sodium dichloroisocyanurate was maintained in a fluidized state. A thermometer was inserted into the fluidized sodium dichloroisocyanurate, at the time when the thermometer showed 68°C, the power supply of the heater was set to OFF, and 12 g of paraffin (melting point 58°C to 60°C) heated to 68°C was added dropwise to the fluidized sodium dichloroisocyanurate for about 30 seconds in a manner to spray. From the start of the addition, a rubber spatula was inserted into the fluidized portion of the sodium dichloroisocyanurate to function as a baffle to promote mixing. The stirring was continued for about 30 seconds from the end of the addition, and then 18 g of fine zeolite warmed to 46°C was added and mixed for about 20 seconds. Air not warmed was blown with an electric blower to cool the sample. The thermometer was inserted into the fluidized sample, and cooled to 40°C or less, to obtain 98 g of the sample. The proportion of the coating layer (mass %) is shown in Table 9. No water was used for the solvent, so no drying step was provided, and the water content was not measured. The sample produced in Comparative Example 11 was subjected to the stability test 1, the foaming test, and the solubility test in the same manner as in the case of Example 1 and Example 2. The results are shown in Table 18.

[0252] (Comparative Example 12)

[0253] Using 61 g of sodium dichloroisocyanurate as a solid bleaching agent, and using 13 g of stearyl alcohol (melting point 59°C) and 26 g of fine zeolite as a coating layer, a sample of 95 g was produced in the same manner as in Comparative Example 11. The proportion of the coating layer (mass %) is shown in Table 9. No water was used for the solvent, so no drying step was provided, and the water content was not measured. The sample produced in Comparative Example 12 was subjected to the stability test 1, the foaming test, and the solubility test in the same manner as in the case of Example 1 and Example 2. The results are shown in Table 18.

[0254]

[0255]

[0256]

[0257]

[0258]

[0259]

[0260]

[0261]

[0262]

[0263]

[0264]

[0265]

[0266]

[0267]

[0268]

[0269]

[0270]

[0271]

[0272] (Examples 40 to 42)

[0273] In addition to the conditions described in Table 19, samples of the solid bleaching agent-containing article having a coating layer were produced using the same method as in Example 1, using a halogenated hydantoin mixture as the solid bleaching agent and using persulfuric acid-sulfuric acid-potassium pentahydrate, trichloroisocyanuric acid, using sodium benzoate for the coating layer, in the same manner as in Example 1. The concentration (mass %) of the coating solution, the water content (mass %) of the produced sample, and the proportion (mass %) of the coating layer are shown in Table 19. For each sample dried at 110°C for 1.5 hours, Stability Test 1, foaming test, and solubility test were performed in the same manner as in the case of Example 1 and Example 2. The results are shown in Table 20. Note that, for Stability Test 1 of Example 41, the effective oxygen retention rate was calculated instead of the effective chlorine retention rate. In addition, for the solubility test of Examples 40 and 42, only the 0.2 mass % test was performed. In any of the examples, the type of the solid bleaching agent was different, but the compound of the coating layer was the same as in Example 1, and the proportion (mass %) of the coating layer was lower than in the case of Example 1, so in the solubility test at 5 mass %, it was confirmed that no residue from the coating layer was produced, and thus the solubility was determined to be O. Note that the solubility of the halogenated hydantoin mixture and trichloroisocyanuric acid in 100 g of water was 0.54 g and 1.2 g, respectively, but a solid bleaching agent having a low solubility in water such as this can also be used.

[0274]

[0275]

[0276] (Examples 43 to 45)

[0277] A sample of the solid bleaching agent-containing article having a coating layer was produced using the same method as in Example 1, using disodium phthalate, sodium benzoate, and sodium 1-naphthoate as the solid bleaching agent, with the conditions described in Table 21 and the heater temperature set to OFF, with no heating, and with the sample left to stand in an oven at 40°C for 1 hour after spraying was complete. The concentration (mass %) of the coating solution is shown in Table 21. The proportion of the coating layer in Examples 43 to 45 was determined using the absorbance method. That is, an aqueous solution of disodium phthalate, sodium benzoate, and sodium 1-naphthoate dissolved at a predetermined concentration was used, and a calibration curve was produced using the absorbance at 280 nm. Using the calibration curve produced, the solid bleaching agent-containing article having a coating layer produced in Examples 43 to 45 was dissolved in water, and disodium phthalate, sodium benzoate, and sodium 1-naphthoate in the aqueous solution were quantified, and the proportion of the coating layer was thus determined. The quantification method is described in more detail below.

[0278] An aqueous solution of disodium phthalate was adjusted to 0.662 (g / L), 0.331 (g / L), 0.166 (g / L), and 0.0828 (g / L). Each of the aqueous solutions was placed in a quartz dish measuring 12.4 mm x 12.4 mm x 45 mm (optical path length 10 mm) and placed on a dish holder of a UV-1800 ultraviolet-visible spectrophotometer (manufactured by Shimadzu Corporation). The absorbance at 280 nm was measured with distilled water as the background, and the results were 1.85, 0.956, 0.490, and 0.252, respectively, and the relationship between the concentration of disodium phthalate and the absorbance was concentration (g / L) = 0.3624 x absorbance - 0.0114. Next, the solid bleaching agent-containing article having a coating layer produced in Example 43 was dissolved so that it became 1.088 (g / L), and an aqueous solution of sodium percarbonate (PC-2) adjusted to the same effective oxygen content was used as the background to measure the absorbance, and the result was 0.881, and it was thus found that the disodium phthalate was 0.308 (g / L). That is, 0.308 g of the 1.088 g was disodium phthalate used in the coating layer, and the proportion of the coating layer was found to be 28 mass % according to the formula 6.

[0279] The same procedure was used to adjust the concentration of a sodium benzoate aqueous solution to 0.582 (g / L), 0.291 (g / L), 0.146 (g / L), 0.0728 (g / L), and measure the absorbance at 280 nm, which resulted in 0.889, 0.463, 0.238, 0.122, respectively. Thus, the relationship between the concentration of sodium benzoate and the absorbance was concentration (g / L) = 0.6655 x absorbance - 0.012. The sample prepared in Example 44 was dissolved in water so as to be 1.112 (g / L), and the effective oxygen content was adjusted to the same amount of sodium percarbonate (PC-2) aqueous solution as the background, and the absorbance was measured in the same manner, which resulted in 0.481. Thus, the sodium benzoate was 0.308 (g / L). That is, 0.308 g in 1.112 g was the sodium benzoate used in the coating layer, and the proportion of the coating layer was calculated to be 28 mass% according to Formula 6.

[0280] The same procedure was used to adjust the concentration of a sodium 1-naphthoate aqueous solution to 0.0504 (g / L), 0.0252 (g / L), 0.0126 (g / L), 0.00630 (g / L), 0.00315 (g / L), and measure the absorbance at 280 nm, which resulted in 1.54, 0.773, 0.387, 0.194, 0.0980, respectively. Thus, the relationship between the concentration of sodium 1-naphthoate and the absorbance was concentration (mass%) = 0.0327 x absorbance - 0.000006. The sample prepared in Example 45 was dissolved in water so as to be 0.1098 (g / L), and the absorbance was 0.844. Thus, the sodium 1-naphthoate was 0.0279 g / L. The proportion of the coating layer was calculated to be 25 mass% according to Formula 6.

[0281] The samples prepared in Examples 43 to 45 were subjected to Stability Test 1, foaming test, and solubility test in the same manner as in Examples 1 and 2. The results are shown in Table 22. Note that, for Stability Test 1 of Examples 43 to 45, the effective oxygen retention rate was calculated instead of the effective chlorine retention rate.

[0282]

[0283]

[0284] Stability Test 2 (Long-term storage test)

[0285] (Examples 46 to 55)

[0286] In a stainless steel beaker, 5 g of distilled water and 3 g of potassium carbonate were placed, and the potassium carbonate was dissolved. Next, while the beaker was heated in hot water, the aqueous solution was stirred, and at the time when the liquid temperature reached 80°C, 50 g of sodium metasilicate pentahydrate, 30 g of trisodium nitrilotriacetate monohydrate, 1 g of sodium olefin-maleic anhydride copolymer, and 10.5 g of sodium sulfate were placed, and the stirring was continued. Thereafter, while the composition, which became a slurry, was stirred, the temperature of the hot water was lowered to 65°C, 0.5 g of sodium metasilicate was placed, and the stirring was continued for 30 minutes, and then the cooling was performed, and a paste-like cleaning agent composition was obtained. Next, the solid bleaching agent-containing substance with the coating layer produced in Examples 2, 3, 5, 6, 7, 13, 14, 20, 21, and 22 and sodium dichloroisocyanurate, which was not subjected to the coating, were accurately weighed in the range of 0.10 g to 0.13 g, respectively, and the mass was recorded to the fourth decimal place, and the weighed substances were placed in a cylindrical polypropylene cup (inner diameter 25 mm, height 22 mm) which was open at the top, and the paste-like cleaning agent composition heated to 60°C was accurately weighed in the range of 2.5 g to 3.5 g, and the mass was recorded to the third decimal place, and the cleaning agent composition containing the solid bleaching agent-containing substance or the solid bleaching agent was produced by adding the cleaning agent composition containing the solid bleaching agent-containing substance or the solid bleaching agent on the solid bleaching agent-containing substance or the sodium dichloroisocyanurate in a stacked manner. The cup to which the cleaning agent composition containing the solid bleaching agent-containing substance or the solid bleaching agent was added was placed in a resin-made basin, the entire basin was placed in a low-density polyethylene bag having a thickness of 0.1 mm, the opening of the bag was closed by heat sealing, and the bag was stored in a constant temperature and humidity chamber at a temperature of 40°C and a relative humidity (RH) of 75% for one month. After one month, the total amount of the cleaning agent composition containing the solid bleaching agent-containing substance or the solid bleaching agent in the cup was dissolved in about 100 ml of distilled water, and the retention rate of the available chlorine was evaluated from the available chlorine content in the same manner as in the case of Stability Test 1.

[0287] In the case of sodium dichloroisocyanurate before coating, the available chlorine was not detected after one month, and the retention rate of the available chlorine was 0%. The retention rate of the available chlorine of the solid bleaching agent-containing substance with the coating layer produced in Examples 2, 3, 5, 6, 7, 13, 14, 20, 21, and 22 was shown in Table 23, and a high retention rate of the available chlorine was also obtained after the long-term storage. Note that in Stability Test 2, the retention rate of the available chlorine of sodium dichloroisocyanurate before coating, which was the reference, was 0%, and therefore the retention rate of the available chlorine of each sample did not become lower than the retention rate of the available chlorine of sodium dichloroisocyanurate before coating. Therefore, unlike the evaluation reference in the case of Stability Test 1, in the case where the retention rate of the available chlorine was less than 5%, the improvement effect of the stability was hardly observed, and therefore the evaluation was not passed, and was marked as x, in the case where the retention rate of the available chlorine was 5% or more, the improvement effect of the stability was observed, and therefore the evaluation was passed, and was marked as o, and in the case where the retention rate of the available chlorine was 70% or more, the evaluation was passed as a special case, and was marked as.

[0288]

[0289] (Examples 56 to 63)

[0290] The solid bleaching agent-containing bodies with coating layers produced in Examples 25, 28, 36, and 37 and the solid bleaching agent-containing bodies with coating layers produced in Examples 31, 35, 38, and 39 were subjected to stability test 2 in the same manner as in Examples 46 to 55. The results are shown in Tables 24 and 25.

[0291]

[0292]

[0293] (Comparative Examples 13 to 16)

[0294] The solid bleaching agent-containing bodies with coating layers produced in Comparative Examples 3, 7, 8, and 11 were subjected to stability test 2 in the same manner as in Examples 56 to 63. The results are shown in Table 26. In Comparative Example 13 (using the solid bleaching agent-containing body produced in Comparative Example 3) and Comparative Example 16 (using the solid bleaching agent-containing body produced in Comparative Example 11), the effective chlorine retention rate in stability test 2 was 1% and 2%, respectively, and the results were lower than in stability test 1. In Comparative Example 14 (using the solid bleaching agent-containing body produced in Comparative Example 7) and Comparative Example 15 (using the solid bleaching agent-containing body produced in Comparative Example 8), the improvement in the effective chlorine retention rate was not observed in stability test 2 as in stability test 1. From the results of stability test 2, it was found that the solid bleaching agent-containing body with coating layer of the present application has a remarkable effect.

[0295]

[0296] Stability Test 3 (abrasion test)

[0297] (Examples 64 to 72)

[0298] To evaluate the stability of the coated solid bleaching agents prepared in Examples 1, 25, 28, 31, 35, 36, 37, 38, and 39 under physical impact, abrasion tests were conducted using a tablet abrasion tester (manufactured by Toyama Sangyo Co., Ltd.). The tablet abrasion tester consists of a plastic barrel-shaped container with an inner diameter of approximately 286 mm and a depth of approximately 38 mm, and an electric motor that rotates the barrel-shaped container vertically. A baffle is provided inside the barrel-shaped container, which raises the test sample inside the container to a height of approximately 157 mm each time the barrel-shaped container rotates, and then lowers it. Such a tablet abrasion tester is readily available; for reference regarding tablet abrasion testers, see the revised reference information of the Japanese Pharmacopoeia at point 17.

[0299] Five g of the coated solid bleaching agent and five g of spherical glass beads (approximately 5 mm in diameter) were placed in the barrel-shaped container of a tablet abrasion tester. The barrel was rotated 1000 times vertically at 25 revolutions per minute using an electric motor. After 1000 rotations, the glass beads were removed from the coated solid bleaching agent. The tablets were then stored in a constant temperature and humidity chamber at 40°C and 75% RH for three months. Otherwise, stability was evaluated using the same method as in stability test 2. When the effective chlorine retention rate was less than 5%, almost no improvement in stability was observed, therefore the result was deemed unacceptable (marked ×). When the effective chlorine retention rate was 5% or higher but less than 10%, an improvement in stability was observed, therefore the result was deemed acceptable (marked ○). When the effective chlorine retention rate was 10% or higher, the result was deemed excellent (marked ◎). The results are shown in Table 27. It is known that even when colliding with glass beads inside a rotating barrel, the solid bleaching contents with the coating layer maintain high stability after being impacted.

[0300] (Comparative Example 17)

[0301] For the solid bleaching agent containing sodium lauryl sulfate in the coating layer prepared under the same conditions as Comparative Example 1, stability tests 3 were conducted using the same method as in Examples 64-72. The results are shown in Table 27. It is believed that the sample prepared in Comparative Example 1 was unable to maintain the effective chlorine retention rate because the solid bleaching agent containing the coating layer was impacted and abraded due to collisions with glass beads inside a rotating drum.

[0302]

[0303] Stability Test 4 (Stirring and Storage Test)

[0304] (Example 73)

[0305] A polypropylene-made resin container (capacity 120 ml, bottom inner diameter 52 mm) with a lid was charged with distilled water 21 g, sodium hydroxide 13 g, sodium metasilicate nonahydrate 5 g, trisodium nitrilotriacetate monohydrate 20 g, diisobutylene-maleic acid copolymer 1 g, sodium carbonate 10 g, sodium hydroxide 30 g, and the solid bleaching agent-containing substance produced in Example 1 2 g in this order, and a Teflon-made stirring blade (stirring blade diameter 40 mm) was used to stir the mixture at 300 rpm for 2 hours in a hot water bath while the inside of the resin container was brought to 40°C, to produce a detergent composition. The total amount of the stirred detergent composition was dissolved in 3 L of distilled water, and the available chlorine content was evaluated. In addition, a container into which the stirred mixture produced in the same manner was put was tightly closed, and left to stand at room temperature for 2 weeks, and the available chlorine content after 2 weeks was similarly evaluated. The stability after stirring was evaluated based on the theoretical available chlorine content calculated from the amount of chlorine agent charged. The results are shown in Table 28. The available chlorine retention rate after stirring the detergent composition for 2 hours was 60% or more of the chlorine agent charged, and the available chlorine content did not decrease after 2 weeks.

[0306] (Comparative Example 18)

[0307] A detergent composition was produced in the same manner as in Example 73 using sodium dichloroisocyanurate (without coating layer) as the solid bleaching agent instead of the solid bleaching agent-containing substance with a coating layer, and stability test 4 was performed. The results are shown in Table 28. No available chlorine was detected at the time after stirring for 2 hours.

[0308]

[0309] Bleaching test

[0310] (Example 74)

[0311] A detergent composition incorporating the solid bleaching agent-containing material with the coating layer produced in Example 73 was dissolved in distilled water to make a 0.2 mass% detergent aqueous solution, and the pH and available chlorine concentration (mg / L) were measured. The results are shown in Table 29. Further, 770 ml of the detergent aqueous solution was put in a 1-L beaker, and 5 cm x 5 cm of cotton cloth (STC EMPA 167, manufactured by Nitto Boseki Co., Ltd.) dyed with black tea was immersed so that half of the cloth area was soaked, and left to stand for 30 minutes at 23°C. The cotton cloth taken out after 30 minutes was dried at room temperature, and then the whiteness of the portion soaked in the detergent aqueous solution and the whiteness of the portion not soaked were evaluated using a whiteness meter (digital whiteness meter TC-6D, manufactured by Tokyo Denshoku Co., Ltd.). The results are shown in Table 29. The whiteness of the portion soaked in the detergent aqueous solution reflects the bleaching effect of the detergent aqueous solution, and the whiteness of the portion not soaked reflects the color of the original cotton cloth, and thus it can be considered that the greater the difference in whiteness between the portions, the higher the bleaching effect exhibited by the detergent aqueous solution. The detergent composition aqueous solution produced in Example 73 had particularly high bleaching power. Note that the greater the numerical value of the whiteness, the closer the color of the object to white. For the whiteness, reference can be made to JIS Z 8715 (Japanese Industrial Standard "Method of Expression of Color, Whiteness"), JIS Z 8722 (Japanese Industrial Standard "Method of Measurement of Color, Reflecting and Transferring Object Color"), and the cotton cloth used in the test can be appropriately selected and used with different dyeing methods and materials. In addition, in the case where a whiteness meter cannot be used, the whiteness can also be evaluated visually.

[0312] (Comparative Examples 19 to 22)

[0313] The whiteness of cotton cloth was evaluated for a detergent aqueous solution (Comparative Example 19) obtained by dissolving the detergent composition produced in Comparative Example 18 in distilled water to make a 0.2 mass%, a 0.2 mass% aqueous solution of the detergent composition produced in the same manner as in Comparative Example 18 except that no solid bleaching agent was added (Comparative Example 20), an aqueous solution (Comparative Example 21) obtained by dissolving only sodium dichloroisocyanurate as a solid bleaching agent in distilled water (the available chlorine concentration was adjusted to be the same as in Example 74), and distilled water alone (Comparative Example 22), in the same manner as in Example 74. The results are shown in Table 29. For the detergent aqueous solution produced from the detergent composition produced in Comparative Example 18, no available chlorine was detected, and thus it was considered that the solid bleaching agent (sodium dichloroisocyanurate) was inactivated at the time of mixing. Further, the detergent composition produced without adding a solid bleaching agent (Comparative Example 20) had the same degree of bleaching effect as the detergent composition produced in Comparative Example 18 (Comparative Example 19), and thus it was considered that even when a solid bleaching agent is incorporated, the bleaching effect is not improved in the case where the solid bleaching agent is inactivated in the detergent composition.

[0314]

[0315] Thus, the detergent composition produced using the solid bleaching agent-containing substance with a coating layer of the present application can maintain effective chlorine even after stirring and mixing, and thus the effective chlorine can act synergistically with other components of the detergent composition, and it is considered that the bleaching effect is higher than any one of the case where the detergent composition does not contain a solid bleaching agent, or the case where a bleaching agent is adjusted to the same effective chlorine concentration.

[0316] As a result of these effects, the solid bleaching agent-containing substance with a coating layer of the present application also exhibits good stability when used in a detergent composition in combination with a detergent component, and can maintain the effects of cleaning, bleaching, and sterilization. In addition, the solid bleaching agent-containing substance of the present application has the effect of foaming, or having little or no residue, and thus can be used in a wider range of applications. It has particularly remarkable effects in terms of having high solubility in water, little or no residue, and exhibiting good stability for a long time in a detergent composition in the presence of water. In addition, the solid bleaching agent-containing substance of the present application also maintains high stability after a physical impact is applied in advance, or after the process of stirring, mixing, or the like of the detergent composition, and has particularly remarkable effects. It is considered that these effects are due to the coating layer of the solid bleaching agent-containing substance inhibiting the reaction of the solid bleaching agent with other components, thereby protecting the solid bleaching agent, and not becoming a factor that causes foaming or residue.

[0317] The present application has been described in detail and with reference to specific embodiments, but it will be apparent to one skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present application. This application is based on Japanese Patent Application (Japanese Patent Application No. 2016-086619) filed on April 22, 2016, the contents of which are incorporated herein by reference.

[0318] Industrial applicability

[0319] The solid bleaching agent-containing substance with a coating layer provided by the present application protects the bleaching agent from factors that cause deterioration, inactivation, or decomposition, and has the effect of improving stability and not causing foaming or residue when used in a detergent composition in combination with various compounds used as a detergent component. Thus, it can be preferably used for cleaning of a drain pipe, a water storage portion, or the like of a kitchen, a bathroom, a washroom, a toilet, or the like, or bleaching, sterilization, and cleaning of tableware, cooking utensils, or the like; washing of clothes or the like; maintenance and management of domestic water such as a bath, a sink, or the like; and the like.

Claims

1. A solid state bleach-containing article having a first layer containing a solid state bleach and a second layer comprising a coating layer, wherein, The coating layer contains one or more selected from the group consisting of alkali metal salts of aromatic carboxylic acids, alkali metal salts of acyclic dibasic carboxylic acids, alkali metal salts of acyclic monobasic carboxylic acids having 1 to 7 carbon atoms, and mixtures thereof, The proportion of the coating layer in the solid bleaching agent-containing product is 5% by mass or more.

2. The solid bleaching agent-containing product according to claim 1, wherein The alkali metal salt of the aromatic carboxylic acid is one or more selected from the group consisting of alkali metal salts of benzoic acid, o-phthalic acid, m-phthalic acid, p-phthalic acid, trimellitic acid, and p-t-butylbenzoic acid, and mixtures thereof.

3. The solid bleaching agent-containing product according to claim 1, wherein The alkali metal salt of the acyclic dibasic carboxylic acid is one or more selected from the group consisting of alkali metal salts of succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, and tetradecanedioic acid, and mixtures thereof.

4. The solid bleaching agent-containing product according to claim 1, wherein The alkali metal salt of the acyclic monobasic carboxylic acid having 1 to 7 carbon atoms is one or more selected from the group consisting of alkali metal salts of formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, and enanthic acid, and mixtures thereof.

5. The solid bleaching agent-containing product according to claim 1, wherein The solid bleaching agent is one or more selected from the group consisting of halogen-containing bleaching agents, oxygen-containing bleaching agents, and mixtures thereof.

6. The solid bleaching agent-containing product according to claim 5, wherein The halogen-containing bleaching agent is 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.

7. The solid bleaching agent-containing product according to claim 5, wherein The oxygen-containing bleaching agent is one or more selected from the group consisting of percarbonate, perborate, peroxymonosulfate, and mixtures thereof.

8. The solid state bleach-containing article of claim 1 wherein, The proportion of the coating layer in the solid bleaching agent-containing product is more than 20% by mass.

9. A cleaning agent composition, comprising: The solid bleaching agent-containing product according to claim 1, and one or more metal ion capturing agents selected from the group consisting of aminocarboxylate, hydrate of aminocarboxylate, hydroxaminocarboxylate, hydrate of hydroxaminocarboxylate, tripolyphosphate, phosphonocarboxylic acid, alkali metal salt of phosphonocarboxylic acid, hydrate of phosphonocarboxylic acid, polyacrylic acid, alkali metal salt of polyacrylic acid, glutamic acid diacetate, hydrate of glutamic acid diacetate, and mixtures thereof.

10. A cleaning agent composition, comprising the solid bleaching agent-containing product according to claim 1 and one or more nonionic surfactants.

11. A cleaning agent composition, comprising the solid bleaching agent-containing product according to claim 1 and one or more alkali metal salts selected from the group consisting of alkali metal hydroxides, alkali metal silicates, alkali metal carbonates, alkali metal phosphates, and mixtures thereof.

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