Cleaning composition and cleaning method

Abstract

The present invention provides a solid cleaning composition containing a high concentration of a solid chlorine bleaching agent and a basic compound for removing firmly adhered moulds, biofilms and other soils, which can inhibit heat generation occurring when the cleaning composition is in contact with a small amount of water, and which can be used in the field of cleaning. The cleaning composition can prevent the container filled with the cleaning composition from being broken due to expansion of the container and the like, and has improved storage stability. Methods of using the solid cleaning compositions are also provided. The present invention relates to a solid cleaning composition comprising: a material comprising a solid chlorine bleaching agent having a coating; and a basic compound. The cleaning composition has an effective chlorine content of 5% or more and a water content of 40 wt.% or less. The 1 wt.% aqueous solution of the cleaning composition has a pH of 9 or higher. The invention also relates to a cleaning method using the cleaning composition.

Description

Technical Field

[0001] The present invention relates to a cleaning composition suitable for cleaning equipment and hard surfaces near water, such as kitchens, bathrooms, toilets, inside drains and washing machine drums, and methods of using the cleaning composition. Background Art

[0002] Various cleaning compositions are used to clean equipment and hard surfaces near water, such as kitchens, bathrooms, toilets, inside drain pipes, and washing machine drums. These containers and hard surfaces are made of various materials, such as ceramics, pottery, tiles, resins, and metals. Such cleaning compositions contain cleaning ingredients, such as bleach and alkaline compounds, which can remove or mask dirt on the items to be cleaned.

[0003] Cleaning compositions containing bleach may cause defects, such as rust on metal surfaces due to the influence of bleach. In order to prevent such defects, a method of further adding a compound with an antiseptic effect to a cleaning composition containing bleach to reduce the corrosiveness to metals can be adopted. For example, patent document (PTL) 1 discloses a cleaning composition for cleaning a washing machine drum, which comprises dichloroisocyanurate and sodium metasilicate pentahydrate that are only subjected to low hydration treatment on the particle surface. PTL 1 describes that the composition can effectively peel off or remove film-like dirt or other dirt composed of, for example, fungi, bacteria and detergents attached to the back of the washing machine drum, and when dissolved in water and used, it also shows low corrosiveness to various metals, and hardly produces a pungent odor.

[0004] Furthermore, even when the composition is stored under relatively high temperature conditions, blocking (solidification) can be suppressed (excellent storage stability).

[0005] In addition, alkaline compounds, such as sodium metasilicate, may cause problems such as degradation of the bleaching agent and reduction of the bleaching effect after contact with the bleaching agent. In order to solve such problems, for example, Patent Document 2 (PTL2) reports a material containing a solid bleaching agent, wherein the particles of the bleaching agent are protected by a coating. PTL2 discloses that in a cleaning composition including such a material containing a solid bleaching agent and an alkaline compound, the bleaching agent is protected from degradation, inactivation and decomposition.

[0006] Reference List

[0007] Patent Literature

[0008] PTL 1:JP2007-217569A

[0009] PTL 2: WO2017 / 183726 Summary of the invention

[0010] Technical issues

[0011] When mold, biofilm and other dirt firmly adhere to areas that cannot be cleaned directly by scrubbing or the like or areas that are difficult to clean on a daily basis, it is often difficult to effectively remove such dirt. The present inventors attempted to prepare a solid cleaning composition containing a solid chlorine bleach and an alkaline compound at a higher concentration than before to remove such firmly adhered dirt.

[0012] However, such solid cleaning compositions containing high concentrations of solid chlorine bleach and alkaline compounds generate considerable heat when in contact with water during use. Such heat generation can lead to problems such as reduced safety during use and corrosion or degradation of the surface of the material to be cleaned. In addition, the presence of water in the cleaning composition can cause the active ingredients to decompose during storage, which can lead to poor cleaning effects, or cause the container containing the cleaning composition to swell and rupture, thereby causing problems such as insufficient storage stability of the cleaning composition. In cleaning compositions containing high concentrations of active ingredients, it is highly desirable to improve these problems.

[0013] Therefore, an object of the present invention is to provide a solid cleaning composition containing a high concentration of solid chlorine bleach and an alkaline compound to remove firmly adhered mold, biofilm and other dirt, which composition can suppress heat generation when in contact with a small amount of water and has improved storage stability, thereby preventing rupture during storage due to, for example, expansion of a container containing the cleaning composition. Another object of the present invention is to provide a method of using the cleaning composition.

[0014] Workaround

[0015] In order to solve the above problems, the inventors have conducted extensive research. As a result, the inventors have found that when a solid cleaning composition includes a material containing a solid chlorine bleaching agent having a coating and an alkaline compound (e.g., metasilicate), and the effective chlorine content is 5% or more, and the water content is 40wt.% or less, and the pH value of the cleaning composition in the form of 1wt.% aqueous solution is 9 or more, the cleaning composition can show a high cleaning effect on stubborn dirt, when the cleaning composition in the form of a high-concentration aqueous solution is in contact with a small amount of water during use, high-temperature heat generation can be effectively suppressed, and deterioration caused by decomposition of active ingredients during storage and rupture caused by expansion of the packaging container can be suppressed, so that the bleaching composition can be stably maintained for a long time.

[0016] The inventors have also found that, in order to enhance the cleaning effect, the cleaning composition of the present invention may also contain other components as additives effective for various cleanings, such as metal ion scavengers, surfactants, polymer dispersants, organic acids, polysaccharides, thickeners and fluorescent whitening agents; and even in this case, the resulting cleaning composition can still achieve the above-mentioned effects.

[0017] Based on these findings, the present invention has been completed after further studies and considerations.

[0018] The present invention provides the following cleaning composition and a cleaning method using the cleaning composition.

[0019] Item 1.

[0020] A solid cleaning composition comprises a solid chlorine bleach material having a coating and an alkaline compound, wherein the effective chlorine content of the cleaning composition is 5% or more, the water content is 40wt.% or less, and the pH value of a 1wt.% aqueous solution of the cleaning composition is 9 or more.

[0021] Item 2.

[0022] The cleaning composition according to item 1, wherein the content of the basic compound (when the basic compound contains bound water, excluding bound water) in the cleaning composition is 5 wt.% or more.

[0023] Item 3.

[0024] The cleaning composition according to item 1 or 2, wherein the sum of the effective chlorine content and the content of the alkaline compound (excluding bound water when the alkaline compound contains bound water) in the cleaning composition is 40 or more.

[0025] Item 4.

[0026] The cleaning composition according to any one of items 1 to 3, wherein the ratio of the effective chlorine content to the alkaline compound content in the cleaning composition (effective chlorine content / alkaline compound content) is in the range of 0.1 to 0.8.

[0027] Item 5.

[0028] The cleaning composition according to any one of items 1 to 4, wherein the alkaline compound is at least one selected from metal metasilicates, metal metasilicate hydrates, metal phosphates, metal phosphate hydrates, and mixtures thereof.

[0029] Item 6.

[0030] The cleaning composition according to any one of items 1 to 5, wherein water derived from the alkaline compound accounts for 60 wt.% or more of the water content of the cleaning composition.

[0031] Item 7.

[0032] The cleaning composition according to any one of items 1 to 6, wherein the water content of the cleaning composition is 32 w t.% or lower.

[0033] Item 8.

[0034] The cleaning composition according to any one of items 1 to 7, wherein the pH value of a 1 wt. % aqueous solution of the cleaning composition is 10.5 or higher.

[0035] Item 9.

[0036] A method for cleaning an article, comprising contacting an aqueous solution of the cleaning composition of any one of items 1 to 8 with the article.

[0037] Beneficial effects of the invention

[0038] The cleaning composition of the present invention comprises a material containing a solid chlorine bleaching agent with a coating and an alkaline compound (e.g., metasilicate) at a high concentration as a bleaching agent, and its water content is within a predetermined range. Based on these characteristics, the cleaning composition of the present invention has a high cleaning (bleaching) effect, can suppress heat generation when the cleaning composition is dissolved in water, and the cleaning composition suppresses expansion and rupture of a packaging container containing the cleaning composition; in addition, the chlorine bleaching agent in the cleaning composition can be stably maintained.

[0039] In the present description, "inhibiting heat generation" means that when water is added to a predetermined amount of a cleaning composition, the maximum temperature reached by the cleaning composition due to heat generation is lower than that of a comparative composition. "Inhibiting expansion and rupture of a packaging container" means that when a cleaning composition is sealed in a predetermined packaging container, the increase in volume of the packaging container is less than that of the same container containing a comparative composition, or the time taken for the packaging container to partially expand and rupture is greater than that of the comparative composition, or the degree of rupture of the packaging container is less than that of the comparative composition. "Stably maintaining chlorine bleach" means that when a cleaning composition is stored for a certain period of time under predetermined conditions, the reduction in the effective chlorine content of chlorine bleach as an active ingredient is less than that of a comparative composition. DETAILED DESCRIPTION

[0040] Cleaning composition

[0041] The cleaning composition of the present invention is suitable for cleaning equipment and hard surfaces near water, such as kitchens, washrooms, toilets, drain pipes, and washing machine drums. The cleaning composition has a good bleaching effect, so it can be used in a variety of scenarios. Examples of equipment and hard surfaces near water include faucets or handles; filters; sinks; triangular corners; cutting boards; tableware; dishwashers; stoves; tripods; ventilating fans, including multi-blade fans (including covers or hood parts); inside drain pipes; microwave ovens; refrigerators; washroom sinks or their surroundings; the water filling part or water tank inside the toilet; bathtubs; drain covers or filters; ceilings, walls, floors, doors, rubber seals or tile joints near water in bathrooms, kitchens, toilets, and washrooms; washing machine drums, drains, lint filters, etc. Other application examples include dentures (including partial dentures).

[0042] When the object to be cleaned is an article that has accumulated water in advance, such as a water injection part of a toilet or a drain, the cleaning method using the cleaning composition of the present invention can be to directly put the cleaning composition into the water. When the object to be cleaned can freely hold water, such as a sink, a bathtub or a washing machine, the cleaning composition can be added after it is filled with water, or water can be added after the cleaning composition is put in. Specifically, the cleaning method of the present invention comprises the following steps: dissolving the cleaning composition in water to prepare an aqueous solution; contacting the target object with the aqueous solution prepared by dissolving the cleaning composition in water.

[0043] When it is necessary to clean the drum of a washing machine, the cleaning composition of the present invention is applicable to both drum-type and vertical washing machines. The cleaning composition can be placed in the drum of the washing machine before water is poured into the drum of the washing machine, or the cleaning composition can be added after the drum of the washing machine is filled with water. The drum of the washing machine can be cleaned using a washing tub cleaning program provided by the washing machine, or the drum of the washing machine can be cleaned using a normal washing program. When cleaning the drum of the washing machine, the aqueous cleaning solution in the drum of the washing machine flows through the lint filter and the drain provided in the washing machine after the drum cleaning program of the washing machine is completed, so that the lint filter and the drain can be cleaned after the drum of the washing machine is cleaned. Alternatively, the lint filter and the drain pipe can be cleaned directly using the cleaning composition.

[0044] When cleaning removable utensils, such as corners, cutting boards, cutlery, hobs, tripods, ventilators, and dentures, the cleaning composition can be placed in a container pre-filled with water to dissolve the composition, and then the target utensil to be cleaned can be soaked in the aqueous solution for cleaning; or the aqueous solution can be poured onto the item to be cleaned. Alternatively, various well-known cleaning methods can be used, such as wiping with a cloth soaked in an aqueous solution of the cleaning composition. Material containing a solid chlorine bleach having a coating

[0045] In the solid chlorine bleach material with coating used in the present invention, the particles of chlorine bleach are protected by the coating. The compound used to form the coating is not particularly limited as long as it can coat the solid chlorine bleach to inhibit the interaction between the solid chlorine bleach and other cleaning ingredients.

[0046] Examples of compounds that can be used to form a coating include carboxylic acid metal salts, surfactants, polysaccharides, higher fatty acids, paraffin waxes, zeolites, and resins. These compounds can be used alone or in combination of two or more. Examples of the use of two or more compounds in combination include: one embodiment is to mix two or more compounds to form a coating containing multiple compounds; and another embodiment is to form a coating layer by using a compound, and then use another compound thereon to form another coating layer to make a multilayer structure. The coating can be formed to completely cover the solid chlorine bleach or can be partially formed, as long as the effect of the present invention is not impaired. Among the compounds that can be used as a coating, carboxylic acid metal salts and surfactants are preferred due to their good solubility in water and excellent stability with solid chlorine bleach. Carboxylic acid metal salts are more preferred because such salts are easy to process into coatings, have excellent functions as coatings in protecting solid chlorine bleach, are easy to obtain and easy to handle.

[0047] Examples of carboxylic acid metal salts include at least one selected from aromatic carboxylic acid metal salts, acyclic dicarboxylic acid metal salts, acyclic monocarboxylic acid metal salts, other carboxylic acid metal salts, and mixtures thereof. The carboxylic acid metal salt may be, for example, a metal salt formed by completely neutralizing the carboxyl group of a carboxylic acid, a metal salt formed by partially neutralizing the carboxyl group of a carboxylic acid, or a carboxylic acid that has not yet formed a metal salt. Based on the use of the metal salt of the carboxylic acid, the material containing the solid chlorine bleach having a coating or the cleaning composition containing the material containing the solid chlorine bleach having a coating can protect the solid chlorine bleach from degradation, deactivation and decomposition, thereby achieving stability.

[0048] Furthermore, the coating formed by adding the carboxylic acid metal salt is stable even when in contact with a solid chlorine bleach, and no adverse side reaction occurs between the solid chlorine bleach and the coating. Therefore, the coating can be provided directly on the surface of the solid chlorine bleach without providing another layer to isolate the solid chlorine bleach from the coating. In addition, the coating containing the carboxylic acid metal salt is preferred because it is not easily agglomerated and has excellent processing properties.

[0049] The metal salt of an aromatic carboxylic acid refers to a metal salt of a compound containing an aromatic ring and a carboxyl group in the compound structure. Preferred examples of metal salts of aromatic carboxylic acids are selected from at least one of metal salts of benzoic acid, phthalic acid (orthophthalic acid), isophthalic acid (isophthalic acid), terephthalic acid (terephthalic acid), trimellitic acid and p-tert-butylbenzoic acid, and mixtures thereof. Examples of metal salts include alkali metal salts, such as lithium salts, sodium salts and potassium salts, and alkaline earth metal salts, such as calcium salts and magnesium salts. In view of ease of availability, alkali metal salts are preferred. In view of solubility in water, sodium salts and potassium salts are more preferred. Particularly preferred examples of metal salts of aromatic carboxylic acids are selected from at least one of alkali metal salts of benzoic acid, alkali metal salts of p-tert-butylbenzoic acid, and mixtures thereof. A preferred example of an alkali metal salt of benzoic acid is sodium benzoate; a preferred example of an alkali metal salt of p-tert-butylbenzoic acid is sodium p-tert-butylbenzoate.

[0050] The metal salt of acyclic dicarboxylic acid refers to a metal salt of a compound that does not have a cyclic structure and contains two carboxyl groups in the compound structure. The example of the metal salt of acyclic dicarboxylic acid is selected from oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, D-tartaric acid, L-tartaric acid, D-malic acid, L-malic acid, D-aspartic acid, L-aspartic acid, glutaric acid, D-glutamic acid, L-glutamic acid, itaconic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecane dioic acid, dodecanedioic acid and tetradecanedioic acid and at least one of the mixture of these metal salts. The example of metal salt includes alkali metal salts, such as lithium salts, sodium salts and potassium salts, and alkaline earth metal salts, such as or calcium salts and magnesium salts. Considering ease of availability, alkali metal salts are preferred. Considering solubility in water, sodium salts and potassium salts are more preferred. Preferred examples of metal salts of acyclic dicarboxylic acids are at least one selected from alkali metal salts of adipic acid, alkali metal salts of sebacic acid, alkali metal salts of undecanedioic acid, alkali metal salts of dodecanedioic acid, and mixtures thereof. Preferred examples of alkali metal salts of adipic acid are disodium adipic acid. Preferred examples of alkali metal salts of sebacic acid are disodium sebacic acid. Preferred examples of alkali metal salts of undecanedioic acid are disodium undecanedioic acid. Preferred examples of alkali metal salts of dodecanedioic acid are disodium dodecanedioic acid.

[0051] "Metal salt of acyclic monocarboxylic acid" refers to a metal salt of a compound having no cyclic structure in the compound structure and containing one carboxyl group. Examples of metal salts of acyclic monocarboxylic acids include metal salts selected from formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, octanoic acid, nonanoic acid, decanoic acid, dodecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, oleic acid, linoleic acid, linolenic acid, acrylic acid, methacrylic acid, isobutyric acid and isovaleric acid, and at least one of mixtures thereof. Examples of metal salts include alkali metal salts, such as lithium salts, sodium salts and potassium salts, and alkaline earth metal salts, such as calcium salts and magnesium salts. In view of ease of availability, alkali metal salts are preferred. In view of solubility in water, sodium salts and potassium salts are more preferred. Preferred examples of metal salts of acyclic monocarboxylic acids are at least one selected from alkali metal salts of heptanoic acid, alkali metal salts of octanoic acid, alkali metal salts of nonanoic acid, alkali metal salts of decanoic acid, alkali metal salts of dodecanoic acid, alkali metal salts of lauric acid, alkali metal salts of myristic acid, alkali metal salts of palmitic acid, alkali metal salts of stearic acid, and mixtures thereof. Preferred examples of alkali metal salts of heptanoic acid are sodium heptanoate. Preferred examples of alkali metal salts of octanoic acid are sodium octanoate. Preferred examples of alkali metal salts of nonanoic acid are sodium nonanoate. Preferred examples of alkali metal salts of decanoic acid are sodium decanoate. Preferred examples of alkali metal salts of dodecanoic acid are sodium dodecanoate. Preferred examples of alkali metal salts of lauric acid are sodium laurate. Preferred examples of alkali metal salts of myristic acid are sodium myristate. Preferred examples of alkali metal salts of palmitic acid are sodium palmitate. Preferred examples of alkali metal salts of stearic acid are sodium stearate.

[0052] The metal salt of other carboxylic acids refers to the metal salt of a compound having a cyclic structure and containing three or more carboxyl groups in the compound structure. A preferred example of the metal salt of other carboxylic acids is a metal salt of citric acid. Examples of metal salts include alkali metal salts, such as lithium salts, sodium salts and potassium salts, and alkaline earth metal salts, such as calcium salts. In view of easy availability, alkali metal salts are preferred. In view of solubility in water, sodium salts and potassium salts are more preferred. A preferred example of the alkali metal salt of citric acid is trisodium citrate.

[0053] The metal salts of aromatic carboxylic acids, metal salts of acyclic dicarboxylic acids, metal salts of acyclic monocarboxylic acids, and metal salts of other carboxylic acids may be used alone or in combination of two or more compounds.

[0054] In the material containing the solid chlorine bleach having a coating, considering the ease of forming the coating on the solid chlorine bleach, the content of the metal salt of carboxylic acid in the coating is preferably 30 wt.% or more, more preferably 50 wt.% or more, and even more preferably 70 wt.% or more, based on the total weight of the coating as 100 wt.%.

[0055] Examples of surfactants that can be used to form the coating include various anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants. Anionic surfactants are preferred in view of ease of availability and excellent stability with solid chlorine bleach. Examples of anionic surfactants include sulfates, such as alkyl sulfates (e.g., sodium lauryl sulfate) and polyoxyethylene alkyl sulfates; sulfonates, such as linear alkylbenzene sulfonates, α-sulfo fatty acid methyl ester salts, α-olefin sulfonates (e.g., sodium α-olefin sulfonate), and dialkyl sulfosuccinates. Among them, sodium lauryl sulfate and sodium α-olefin sulfonate are preferred in view of good stability with chlorine bleach and ease of handling as a coating.

[0056] In the material containing the solid chlorine bleach having a coating, the surfactant content of the coating is preferably 5 wt.% or more, more preferably 20 wt.% or more, even more preferably 50 wt.% or more, based on the total weight of the coating being 100 wt.%, in consideration of the ease of forming the coating on the solid chlorine bleach. A combination of a metal salt of a carboxylic acid and a surfactant may also be used to form the coating.

[0057] The coating may contain various compounds, such as inorganic compounds and organic compounds, as long as these compounds do not impair the effects of the present invention. Examples of inorganic compounds include, but are not limited to, phosphates, sulfates, silicates, chlorides, iodides, and bromides; examples of organic compounds include, but are not limited to, polysaccharides, polymer compounds, and salts of organic compounds.

[0058] In view of obtaining a stabilizing effect on the solid chlorine bleach by the coating, the ratio (wt.%) of the coating in the material containing the solid chlorine bleach having a coating is preferably in the following range: based on the total weight of the material containing the solid chlorine bleach having a coating as 100 wt.%, the lower limit is preferably 5 wt.% or more, more preferably 10 wt.% or more, even more preferably 15 wt.% or more. In view of obtaining a sufficient stabilizing effect on the solid chlorine bleach without excessively increasing the ratio of the coating, the upper limit is preferably 70 wt.% or less, more preferably 50 wt.% or less, even more preferably 45 wt.% or less.

[0059] To calculate the proportion of the coating in a material containing a solid chlorine bleach having a coating, a calculation method according to the following formula 1 can be used.

[0060] Coating ratio (wt.%) = Q1×100 / Q2 (Formula 1)

[0061] Q1: Weight of coating in materials containing solid chlorine bleach with coating (g)

[0062] Q2: Weight of material containing coated solid chlorine bleach (g)

[0063] For example, when 1 g of the material containing the solid chlorine bleach having a coating layer contains 0.3 g of the coating layer, the ratio (wt.%) of the coating layer is calculated as 30 wt.% by 0.3 x 100 / 1 = 30 according to Formula 1. The weight of the coating layer in the material containing the solid chlorine bleach having a coating layer can be determined, for example, by dissolving the material containing the solid chlorine bleach having a coating layer in a solvent such as water and analyzing the solution by a known analytical method such as liquid chromatography to quantify the weight of the compound used in the coating layer, or by subtracting the weight of the solid chlorine bleach from the weight of the material containing the solid chlorine bleach having a coating layer. The weight of the solid chlorine bleach can be determined by using a known analytical method such as liquid chromatography.

[0064] Identification and quantification of the coating can be performed by known measurement methods. For example, if the absorbance of the compound used to form the coating is known, the proportion (wt.%) of the coating can be calculated by adjusting the compound used in the coating to a known concentration and creating a calibration curve (absorbance method), or by measuring by well-known methods such as liquid chromatography or gas chromatography. When quantification of solid chlorine bleach is easier than quantification of the coating, the weight of the coating can be calculated based on the weight of the solid chlorine bleach.

[0065] The coating ratio can be calculated from the available chlorine content of the material containing solid chlorine bleach according to the following formula 2:

[0066] Coating ratio (wt.%) = (P1-P2) × 100 / P1 (Formula 2)

[0067] P1: Available chlorine content of solid chlorine bleach used as starting material (%)

[0068] P2: Available chlorine content of material containing coated solid chlorine bleach (%)

[0069] Specifically, for example, when sodium dichloroisocyanurate having an effective chlorine content of 64.5% is used as a solid chlorine bleach to produce a material containing a solid chlorine bleach having a coating, if the effective chlorine content of the material containing the solid chlorine bleach having a coating is 40.0%, then the ratio of the coating calculated according to Formula 2 is 38.0%.

[0070] The content of surfactant and metal salt of carboxylic acid in the coating of the material containing solid chlorine bleach with a coating can be determined by using known analytical methods, such as liquid chromatography. For example, if the content of surfactant or metal salt of carboxylic acid in the material containing solid chlorine bleach with a coating is 5 wt.%, and the coating accounts for 30 wt.% of the material containing solid chlorine bleach with a coating, then the content of surfactant or metal salt of carboxylic acid in the coating is calculated to be 16.7 wt.%, based on the total weight of the coating being 100 wt.%.

[0071] The method for quantifying the proportion of the coating layer in the material containing the solid chlorine bleach having a coating layer and the content of the compound in the coating layer may be any of the above methods or any appropriate known method. Even if there are errors in the results obtained by some of the measuring methods, as long as the value obtained by any of the measuring methods falls within the prescribed range, even if the results obtained by other measuring methods fall outside the prescribed range, it can be considered to meet the requirements.

[0072] In addition to the material containing the solid chlorine bleach with a coating, the cleaning composition may contain another solid bleach without a coating (which may be simply referred to as a solid bleach) as long as the effect of the present invention is not impaired. When the cleaning composition contains the solid bleach, the ratio of the content of the solid bleach to the content of the material containing the solid chlorine bleach with a coating in the cleaning composition (the content of the solid bleach / the content of the material containing the solid chlorine bleach with a coating) is preferably 1 or less, more preferably 0.8 or less, and even more preferably 0.5 or less. Such a content ratio is preferred because a content ratio of 1 or less means that the content of the material containing the solid chlorine bleach with a coating in the cleaning composition is equal to or higher than the content of the solid bleach (without a coating), whereby the heat generation of the material containing the solid chlorine bleach with a coating can be suppressed to a low level, and the cleaning composition tends to easily obtain an excellent storage stability effect, and is more economically advantageous than a cleaning composition consisting entirely of a material containing the solid chlorine bleach with a coating.

[0073] Cleaning compositions containing solid chlorine bleach have excellent cleaning, disinfection and bleaching effects.

[0074] In addition to solid chlorine bleach, the cleaning composition may also include oxygen bleach, as long as the effect of the present invention is not impaired. Examples of oxygen bleach include sodium percarbonate, sodium perborate, organic peroxides such as benzoic acid peroxide, and double salts of monopotassium persulfate. In view of easy availability and operability, sodium percarbonate and sodium perborate are preferred. These oxygen bleaches may be used alone or in combination of two or more.

[0075] Examples of solid chlorine bleaches include trichloroisocyanuric acid, sodium dichloroisocyanurate, sodium dichloroisocyanurate hydrate, potassium dichloroisocyanurate, dichlorohydantoin, chlorobromohydantoin, calcium hypochlorite, and crystalline sodium hypochlorite. In view of excellent bleaching effect, easy handling, and availability, trichloroisocyanuric acid, sodium dichloroisocyanurate, and sodium dichloroisocyanurate hydrate are more preferred. These solid chlorine bleaches may be used alone or in combination of two or more.

[0076] The effective chlorine content (in terms of Cl2) of solid chlorine bleach can be calculated by iodine titration. That is, the iodine released by the reaction of active chlorine and potassium iodide is titrated with sodium thiosulfate aqueous solution, and the effective chlorine content is calculated according to the following formula 3.

[0077] Effective chlorine content % = a × f × 0.35452 / b (Formula 3)

[0078] a: Titration requires 0.1N sodium thiosulfate aqueous solution (ml)

[0079] b: Sample (g)

[0080] f: coefficient of 0.1N sodium thiosulfate aqueous solution

[0081] The theoretical effective chlorine content of trichloroisocyanuric acid is 91.5%, the theoretical effective chlorine content of sodium dichloroisocyanurate is 64.5%, and the theoretical effective chlorine content of sodium dichloroisocyanurate dihydrate is 55.4%.

[0082] Taking into account the addition of compounds that can be used as cleaning agents, such as alkaline compounds, water and other additives, while the cleaning composition has an effective chlorine content of a certain level or higher, the content of the material containing the solid chlorine bleach having a coating in the cleaning composition is preferably 5 wt.% to 80 wt.%, more preferably 10 wt.% to 70 wt.%, even more preferably 15 wt.% to 60 wt.%, still even more preferably 20 wt.% to 60 wt.%, and most preferably 30 wt.% to 60 wt.%, based on the total weight of the entire cleaning composition being 100 wt.%.

[0083] In view of obtaining good cleaning and bleaching effects, the effective chlorine content of the cleaning composition containing solid chlorine bleach must be 5% or more, preferably 6% or more, more preferably 10% or more, even more preferably 13% or more, and even more preferably 15% or more. In view of the fact that additives other than solid chlorine bleach are added to the cleaning composition when it has sufficient effective chlorine content, the effective chlorine content of the cleaning composition is preferably 70% or less, more preferably 50% or less, even more preferably 40% or less. The higher the effective chlorine content in the cleaning composition, the more intense the heat generated when water is added. In particular, in view of inhibiting heat generation, the cleaning composition of the present invention is used as a cleaning composition with a high effective chlorine content, thereby providing a significant inhibitory effect on heat generation, and therefore has great significance. The effective chlorine content (in terms of Cl2) of the cleaning composition can also be calculated by iodine titration, just like the effective chlorine content of the above-mentioned chlorine bleach. Specifically, the iodine released by the reaction of active chlorine with potassium iodide is titrated with an aqueous sodium thiosulfate solution, and the effective chlorine content is calculated according to the above formula 3.

[0084] The method for manufacturing a material containing a solid chlorine bleaching agent having a coating layer can adopt a known coating method. As a manufacturing device, at least one device selected from a stirring device, a rolling granulation device, a fluidized bed granulation device, and a combination of these devices can be used. Each of the multiple steps can be performed by using different processing equipment. Considering the ease of processing, it is preferred to select at least one device from a rolling granulation device, a fluidized bed granulation device, and a combination of these devices. Alternatively, the manufacturing method described in Patent Document 2 (PTL2) can also be used.

[0085] The material containing the solid chlorine bleach having a coating is preferably in the form of a powder or granules. The average particle size of the material is preferably 1 to 5000 μm, more preferably 10 to 3000 μm, and even more preferably 100 to 1500 μm. The average particle size can be measured by using the method for measuring the average particle size of a cleaning composition powder described below. Alternatively, the average particle size can also be measured using the method described in Patent Document 2 (PTL 2).

[0086] Basic compounds

[0087] In this specification, "alkaline compound" refers to a metal salt of an inorganic compound or an organic compound that exhibits alkalinity when dissolved in water. Examples of alkaline compounds include at least one selected from metal silicates, metal phosphates, alkali metal hydroxides, alkaline earth metal hydroxides, carbonates, hydrates thereof, and mixtures thereof. Preferred examples of metal salts are alkali metal salts and alkaline earth metal salts. In view of alkalinity strength, ease of availability and ease of handling, the alkaline compound is preferably an alkali metal salt. Among alkali metal salts, sodium salts and potassium salts are particularly preferred in view of solubility in water and ease of availability. The cleaning composition may contain a combination of two or more alkaline compounds.

[0088] Examples of alkali metal hydroxides include at least one selected from lithium hydroxide, sodium hydroxide, potassium hydroxide, and mixtures thereof. Examples of alkaline earth metal hydroxides include at least one selected from beryllium hydroxide, calcium hydroxide, magnesium hydroxide, and mixtures thereof. Examples of carbonates include at least one selected from sodium carbonate (hereinafter referred to as "soda ash"), sodium bicarbonate (hereinafter referred to as "baking soda"), potassium carbonate, potassium bicarbonate, ammonium carbonate, sodium sesquicarbonate, and mixtures thereof.

[0089] Among these alkaline compounds, preferred metal silicates and metal phosphates. Preferred examples of metal silicates include at least one selected from metal orthosilicates, metal orthosilicate hydrates, metal metasilicates, metal metasilicate hydrates, and mixtures thereof. Examples of metal phosphates include at least one selected from metal hydrogen phosphates, metal phosphates, metal pyrophosphates, metal tripolyphosphates, metal tetrapolyphosphates, metal pentapolyphosphates, metal metaphosphates, hydrates thereof, and mixtures thereof. The metal salt is preferably a metal salt of an alkali metal or an alkaline earth metal. In view of alkaline strength, availability and ease of handling, preferred alkali metal salts. Among alkali metal salts, in view of solubility and availability in water, particularly preferred sodium salts and potassium salts.

[0090] In view of easy handling, easy availability and alkalinity strength, the metal silicate is preferably sodium metasilicate and sodium metasilicate hydrate. The sodium metasilicate hydrate is more preferably at least one of sodium metasilicate pentahydrate, sodium metasilicate nonahydrate, and a mixture thereof.

[0091] Considering the ease of handling, availability and alkalinity strength, the phosphate metal salt is preferably sodium tripolyphosphate, sodium diphosphate, sodium metaphosphate, and hydrates thereof. The sodium diphosphate hydrate is preferably sodium diphosphate decahydrate. These silicate metal salts and phosphate metal salts can be used alone or in combination of two or more.

[0092] The cleaning composition of the present invention containing the alkaline compound has excellent effects of stain removal, bleaching, etc. due to alkalinity.

[0093] In view of enhancing the effects of alkalinity-based stain removal and bleaching, etc., and in view of providing a higher cleaning effect than that achieved by using only the alkaline compound based on the presence of the solid chlorine bleach and the alkaline compound, the content of the alkaline compound (if the alkaline compound contains bound water, the bound water is excluded) in the cleaning composition is generally 5 wt.% or more, preferably 5 to 90 wt.%, more preferably 10 to 80 wt.%, and even more preferably 15 to 75 wt.%, based on the total weight of the entire cleaning composition as 100 wt.%.

[0094] The alkaline compound is usually solid, preferably in the form of powder or granules. The average particle size of the alkaline compound is preferably 1 to 5000 μm, more preferably 10 to 3000 μm, and further preferably 100 to 2000 μm. The average particle size can be measured using the following method for measuring the average particle size of the cleaning composition powder.

[0095] Ratio of available chlorine content to alkaline compound content in cleaning composition

[0096] The solid chlorine bleach and alkaline compound in the cleaning composition of the present invention are both essential components of the cleaning composition of the present invention, which contribute to the cleaning effect. In addition, the available chlorine provided by the solid chlorine bleach and the alkalinity provided by the alkaline compound are considered to contribute to cleaning respectively according to their different effects. Therefore, if the content of only one of the two components is too high, the effect of the present invention may not be fully obtained. Therefore, the ratio of the available chlorine content to the alkaline compound in the cleaning composition is preferably within a certain range. The ratio of the available chlorine content to the alkaline compound content is defined as the available chlorine content (%) of the cleaning composition divided by the content (wt.%) of the alkaline compound in the clean cleaning composition (excluding bound water). In view of obtaining a high cleaning effect, the ratio of the available chlorine content to the alkaline compound content is preferably within the range of 0.1 to 0.8, more preferably 0.15 to 0.75, further more preferably 0.2 to 0.7, even more preferably 0.25 to 0.7, and most preferably 0.3 to 0.7.

[0097] The sum of the available chlorine content and the alkaline compound content in the cleaning composition

[0098] Since the solid chlorine bleach and the alkaline compound in the cleaning composition of the present invention are both essential components of the cleaning composition of the present invention and contribute to the cleaning effect, both components are preferably present in the cleaning composition in a predetermined amount or more. The sum of the available chlorine content and the alkaline compound content in the cleaning composition can be defined by adding the available chlorine content (%) in the cleaning composition to the net alkaline compound content (wt.%) excluding bound water. In view of obtaining a high cleaning effect, the sum of the available chlorine content and the alkaline compound content in the cleaning composition is preferably 40 or more, more preferably 45 or more, further more preferably 50 or more, even more preferably 55 or more, and most preferably 60 or more.

[0099] Water content of cleaning composition

[0100] The water present in the cleaning composition may be present in the form of free water or bound water. Free water and bound water may be present in the form of a mixture. Free water and bound water may be interchangeable. In this specification, "water content" refers to the total content of free water and bound water. Although water may exist in a variety of forms, such as free water and bound water, in order to maintain the solid state of the composition and improve storage stability, it is preferably present in the form of bound water. In this specification, "bound water" refers to water in a state where water molecules are bound to a compound through hydrogen bonds. Although bound water is sometimes referred to as hydrated water, crystallized water, etc., bound water, hydrated water and crystallized water have the same meaning.

[0101] Examples of metal silicates include sodium metasilicate pentahydrate and sodium metasilicate nonahydrate. The water molecules in these compounds exist in the form of being added to sodium metasilicate, such as pentahydrate and nonahydrate, and can be regarded as bound water. For example, the molecular weight of sodium metasilicate is 122.06, the molecular weight of sodium metasilicate pentahydrate is 212.14, and the molecular weight of water molecules (pentahydrate) in sodium metasilicate pentahydrate is 90.08. The water content of sodium metasilicate pentahydrate calculated by 90.08 / 212.14x100 is 42.46wt.%. Therefore, if the cleaning composition contains 50.0wt.% of sodium metasilicate pentahydrate, the water content from sodium metasilicate pentahydrate in the cleaning composition is 21.2wt.%. Similarly, when the water content of sodium metasilicate nonahydrate is calculated to be 57.06 wt.%, if the cleaning composition contains 50.0 wt.% of sodium metasilicate nonahydrate, the water content from the sodium metasilicate nonahydrate in the cleaning composition is 28.5 wt.%.

[0102] When a compound with unknown water content is included as a raw material, the water content of the raw material can be defined by the weight loss when the raw material is dried to a constant weight using a constant temperature dryer, a heating furnace or a thermogravimetric-differential thermal analyzer (which may be referred to as TG-DTA), or can be calculated according to the following formula 4.

[0103] Water content (wt.%) = (W2-W1) × 100 / W2 (Formula 4)

[0104] W1: Weight of sample after drying (g)

[0105] W2: weight of sample before drying (g)

[0106] The water content of a material containing a solid chlorine bleach with a coating can be measured, for example, by the following method. A predetermined amount of the solid chlorine bleach material with a coating is placed on a baking tray coated with enamel paint, the baking tray is placed in a heating furnace set at 110° C., and then the solid chlorine bleach material with a coating is heated and dried to a constant weight. The water content is calculated according to Formula 4 using the weight loss of the solid chlorine bleach material with a coating. Under normal pressure, when heated and dried at a temperature close to the boiling point of water, free water evaporates. Therefore, for free water, the water content can be determined by heating and drying at a relatively low temperature of about 100° C.

[0107] The water content of the basic compound can be measured by, for example, the following method. The weight loss of the basic compound is calculated by TG-DTA according to Formula 4 using the weight loss obtained by heating the basic compound to, for example, 300° C. at a predetermined heating rate. For bound water, water in the compound may not be removed from the compound unless heated to a temperature higher than the boiling point of water. Therefore, heating to a relatively high temperature is necessary in some cases.

[0108] The water content of the cleaning composition can be determined based on the water content and content ratio of each starting material in the cleaning composition. By measuring the water content of each starting material before adding the starting material to the cleaning composition, the water content in the cleaning composition can be obtained based on the water content and content ratio of each starting material. Alternatively, the water content can also be measured from the cleaning composition. When the cleaning composition is heated, if the bleach, alkaline compound or other additives decompose and react when heated, the water content may not be accurately measured. Therefore, it is desirable to measure the water content at a temperature lower than the decomposition of each starting material. The method for quantifying the water content in the cleaning composition can be appropriately selected from the above method or known methods. Even if there is an error in the result obtained by the measurement method, if the value of the result obtained by any one of the measurement methods falls within a predetermined range, then even if the results measured by other measurement methods fall outside the predetermined range, it can also be considered to meet the requirements.

[0109] When the water content in the cleaning composition is higher than a predetermined amount, although the effect of suppressing heat generation when water is added to the cleaning composition can be obtained, the amount of effective ingredients directly contributing to cleaning in the cleaning composition, such as solid chlorine bleach and alkaline compounds, is relatively reduced, and the packaging container of the cleaning composition is also more likely to swell and rupture, thereby reducing storage stability. Therefore, the water content of the cleaning composition must be 40 wt.% or less, preferably 32 wt.%, and more preferably 28 wt.% or less.

[0110] On the other hand, when the water content of the cleaning composition is lower than a predetermined amount, the expansion and rupture of the packaging container of the cleaning composition can be suppressed. Therefore, the water content of the cleaning composition can be 0wt.% (i.e., it does not contain water). However, in order to fully obtain the effect of suppressing heat generation after adding water to the cleaning composition, the water content in the cleaning composition is preferably 0.1wt.% or higher, more preferably 0.8wt.% or higher, further preferably 5wt.% or higher, and particularly preferably 10wt.% or higher.

[0111] That is, the water content of the cleaning composition is preferably within a specified range in view of suppressing heat generation when water is added to the cleaning composition, suppressing expansion and rupture of a packaging container containing the cleaning composition, and maintaining the effective chlorine content as an active ingredient of a bleaching agent in the cleaning composition for a long period of time.

[0112] The water in the cleaning composition may be in the form of free water or bound water. The source of water may be selected from various sources, such as free water or bound water in the compounds contained in the cleaning composition. The water is preferably from bound water contained in the alkaline compound. The mechanism for suppressing heat generation after adding water to the cleaning composition may be the synergistic effect of the following factors: based on the use of a material containing a solid chlorine bleach with a coating, the reaction between the solid chlorine bleach and the alkaline compound is suppressed; and the accumulation of heat is suppressed by the moisture previously contained in the composition. Therefore, the bound water directly combined with the alkaline compound as a heat generation source may play an important role. With respect to the water content in the cleaning composition, the proportion of water from the bound water contained in the alkaline compound is preferably higher. Based on the total weight of the water content of the cleaning composition as 100wt.%, the proportion of water (bound water) from the alkaline compound is preferably 60wt.% or higher, more preferably 70wt.% or higher, and further preferably 80wt.% or higher. Note that the effect of the present invention is not limited by this inferred mechanism.

[0113] Dosage form of coating composition

[0114] The cleaning composition of the present invention is solid and can be formulated into powder, tablet or solid dosage form. Powder, tablet and solid dosage form can also be used in combination. In addition, powder, tablet and solid can all be formed into a composition containing several ingredients. Some ingredients can be made into powder, and specific ingredients that are the same or different from the powder can be made into tablet or solid, or powder and tablet or solid can be used in combination. Considering rapid dissolution in water and exerting efficacy, the cleaning composition of the present invention is preferably made into powder. The powder can be prepared by mixing powder raw materials containing a material containing a solid chlorine bleach with a coating and multiple components of an alkaline compound using a mixer or similar well-known methods, or omitting the mixing step and directly putting multiple starting materials into packaging materials to prepare.

[0115] In this specification, "powder" refers to a cluster of particles. The shape of the particles is not particularly limited, including, for example, irregular, spherical and spheroidal shapes. Examples of powders include those obtained by secondary processing of powders into particles, for example, examples of fine powders processed by known methods such as fluidized bed granulation, or examples of fine powders compressed and then crushed by known methods such as Chilsonator. The starting compounds can be pre-mixed and then subjected to secondary processing, such as granulation; or the starting compounds can be pre-processed, such as granulation, and then mixed to prepare the cleaning composition.

[0116] The average particle size of the powder is preferably 1 to 5000 μm, more preferably 10 to 3000 μm, and further more preferably 100 to 1500 μm. If the average particle size is 5000 μm or less, the cleaning composition in powder form is not too large and is easy to handle. In addition, when used directly for cleaning or bleaching, the powder is easy to use because it can be directly put into a drain with a small opening, etc. When the average particle size is 1 μm or more, the powder is easy to use because it is not easily blown away by breeze or static electricity during handling.

[0117] The average particle size can be measured in the following manner. By using 13-level sieves and receiving trays 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 and 2000 μm, the individual sieves of the sieve are stacked on top of the receiving tray in a manner where the sieve with a larger mesh size is located on the upper layer. The sample is placed on the topmost sieve with a mesh size of 2000 μm, and the sieve is stacked on top of the receiving tray in a manner where the sieve with a larger mesh size is located on the upper layer. The stacked sieves are placed on a sieve shaker and shaken for 10 minutes for screening. The sieve shaker is used at a frequency of 3600 times / minute and an amplitude of 1 mm. The determination of particle size distribution can be carried out using the methods and instruments (sieves) described in JIS Z 8815 and JIS Z 8801.

[0118] Examples of sieve shakers that can be used include, but are not limited to, the "AS200 Control" produced by Retsch. When a sieve shaker is not available, support the stacked sieves with one hand and tap the sieve frame at a rate of about 120 times per minute. Sometimes the sieves are placed horizontally and the sieve frame is tapped vigorously several times. Repeat this operation to fully screen the sample. In the case where the sample is agglomerated due to static electricity, etc., or in the case where fine powder adheres to the inside or back of the sieve, gently loosen the sample with a brush and repeat the sieving operation. Samples that have passed through the sieve are considered to have been sieved. Sieving means that the test sample has passed through the sieve at the end of screening.

[0119] In the case where the sample contains particles with a particle size greater than 2000 μm, multiple layers of sieves with gradually larger mesh sizes exceeding 2000 μm can be added. For example, sieves with mesh sizes of 2360 μm, 2800 μm, 3350 μm, 4000 μm, 4750 μm, 5600 μm or larger can be added. In the case where the sample contains a large number of particles with a particle size of 75 μm or smaller, sieves with gradually smaller mesh sizes below 75 μm can be added. For example, sieves with mesh sizes of 63 μm, 53 μm, 45 μm, 38 μm or smaller can be added. Sieves with other mesh sizes can also be selected.

[0120] Measure the weight of the particles remaining on each sieve and the receiving tray, and calculate the weight percentage (%) of the particles on each sieve. The weight percentage of the particles is accumulated by adding the weight percentages of the particles on the sieves with smaller meshes in increasing order starting from the receiving tray. Assuming that the mesh of the first sieve that reaches a cumulative weight percentage of 50% or more is aμm, the mesh of the sieve one level larger than aμm is bμm, the cumulative weight percentage from the receiving tray to the sieve with a mesh of aμm is c%, and the weight percentage of the particles on the sieve with a mesh of aμm is d%, then the average particle size can be obtained according to the following formula 5.

[0121] Average particle size (μm) = 10 S (Formula 5)

[0122]

[0123] pH of the aqueous solution of the cleaning composition

[0124] Due to the relatively high concentration of the alkaline compound, the cleaning composition of the present invention has an alkaline pH value when dissolved in water. A 1 wt.% aqueous solution of this cleaning composition has a pH value of 9 or higher. In view of better removal of dirt based on alkalinity and enhanced cleaning effects such as bleaching, a 1 wt.% aqueous solution of the cleaning composition of the present invention has a pH value of 9 or higher, preferably a pH value of 10 or higher, more preferably a pH value of 10.5 or higher, and further more preferably a pH value of 11.5 or higher.

[0125] Other additives

[0126] Cleaning compositions of the present invention can also contain various compounds that are conducive to cleaning. Cleaning compositions of the present invention can contain other additives, such as organic acids, surfactants, chelating agents (metal ion scavengers), organic polymers, spices, dyes, enzymes and inorganic substances, as long as the effect of the present invention is not impaired. Except solid additives, liquid additives can also be used. For example, liquid additives can be mixed with porous inorganic powders such as zeolite in advance, and the liquid component is loaded on the inorganic substance, and then added.

[0127] Examples of organic acids include, but are not limited to, at least one selected from oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, D-tartaric acid, L-tartaric acid, D-malic acid, L-malic acid, D-aspartic acid, L-aspartic acid, glutaric acid, D-glutamic acid, L-glutamic acid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, myristic acid, stearic acid, palmitic acid, citric acid, and mixtures thereof. Considering that it is solid and easy to handle at room temperature and pressure, examples of organic acids are preferably selected from at least one selected from oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, D-tartaric acid, L-tartaric acid, D-malic acid, L-malic acid, D-aspartic acid, L-aspartic acid, glutaric acid, D-glutamic acid, L-glutamic acid, citric acid, and mixtures thereof. In view of the excellent mixing stability of solid chlorine bleaching agents such as sodium dichloroisocyanurate (hypochlorous acid generating source), a more preferred example of the organic acid is at least one selected from succinic acid, fumaric acid, and a mixture thereof.

[0128] Examples of surfactants that can be used include anionic surfactants, nonionic surfactants, cationic surfactants and amphoteric surfactants, etc. In view of the ease of availability, anionic surfactants are preferred. The addition of surfactants not only helps the contact of cleaning ingredients with the object to be cleaned, but the surfactant itself also helps to remove dirt on the object to be cleaned.

[0129] When the coating layer of the material containing the solid chlorine bleach having a coating layer contains a surfactant, the content of the surfactant (including the surfactant contained in the coating layer) in the cleaning composition is preferably 0.1 wt.% or more, more preferably 1 wt.% or more, further more preferably 2 wt.% or more, based on the weight of the cleaning composition, in view of obtaining a sufficient surfactant effect and increasing the amount of foaming.

[0130] Too high a surfactant content will result in little contribution to cleaning, and the content of other cleaning ingredients will also be limited. Therefore, the surfactant content in the cleaning composition is preferably 20 wt.% or less, more preferably 10 wt.% or less, and further more preferably 8 wt.% or less, based on the weight of the cleaning composition.

[0131] Alternatively, the surfactant may not be added to the cleaning compositions, but may be added separately to the water-filled part of the article to be cleaned. For example, the surfactant may be added in advance to the water-filled part in contact with the article to be cleaned, and then the cleaning compositions may be added. In this case, the amount of the surfactant added separately is not particularly limited, and may be, for example, within the same range as the situation in which the surfactant is added to the cleaning compositions. The example of available surfactant is at least one selected from anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, and mixtures thereof.

[0132] Examples of the anionic surfactant include at least one selected from the group consisting of fatty acid salts such as potassium oleate soap, potassium castor oil soap, semi-hardened tallow fatty acid sodium soap, and semi-hardened tallow fatty acid potassium soap; alkyl sulfate ester salts such as sodium lauryl sulfate, sodium high alcohol sulfate, triethanolamine lauryl sulfate, and ammonium lauryl sulfate; alkyl benzene sulfonates such as C 12 -C 14 Sodium alkylbenzene sulfonate, branched or linear; sulfonates, such as C 14 -C 18 Sodium α-olefin sulfonate; alkylnaphthalene sulfonates, such as sodium alkylnaphthalene sulfonate; dialkyl sulfonyl succinates, such as sodium dialkyl sulfonyl succinate; alkyl diaryl ether sulfonates, such as sodium alkyl diphenyl ether disulfonate; alkyl phosphates, such as potassium alkyl phosphates; naphthalenesulfonic acid formaldehyde condensates, such as the sodium salt of β-naphthalenesulfonic acid formaldehyde condensate; aromatic sulfonic acid formaldehyde condensates, such as the sodium salt of aromatic sulfonic acid formaldehyde condensates; polyoxyethylene alkyl ether sulfate ester salts, such as sodium polyoxyethylene lauryl ether sulfate; alkyl sulfonyl succinates, such as sodium alkyl sulfonyl succinate; and mixtures of these.

[0133] Examples of the nonionic surfactant include at least one selected from the following: alkyl ethers such as lauryl alcohol alkoxylates, lauryl alcohol ethoxylates, oleyl alcohol ethoxylates and primary alcohol ethoxylates; polyoxyethylene alkyl ethers such as polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether and polyoxyethylene higher alcohol ether; EO-PO block polymers such as polyoxyethylene-polyoxypropylene block polymers, reversed polyoxyethylene-polyoxypropylene block polymers, polyoxyethylene-polyoxypropylene condensates, polyoxyethylene-polyoxypropylene block polymers of ethylenediamine, reversed polyoxyethylene-polyoxypropylene block polymers of ethylenediamine; sorbitan fatty acid esters such as sorbitan laurate, sorbitan palmitate, sorbitan stearate and sorbitan oleate; polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan stearate and polyoxyethylene sorbitan oleate; Oxyethylene sorbitan palmitate, polyoxyethylene sorbitan stearate and polyoxyethylene sorbitan oleate; polyethylene glycol fatty acid esters, such as polyethylene glycol laurate, polyethylene glycol stearate and polyethylene glycol oleate; polyoxyethylene alkylamines, such as polyoxyethylene lauramine, polyoxyethylene stearylamine and ethylenediamine-polyoxyethylene-polyoxypropylene block polymers; alkyl alkanolamides, such as lauric acid monoethanolamide, lauric acid diethanolamide, myristic acid monoethanolamide, myristic acid diethanolamide, stearic acid monoethanolamide, stearic acid diethanolamide, coconut oil fatty acid monoethanolamide and coconut oil fatty acid diethanolamide; glycerol fatty acid esters, such as stearic acid monoglyceride, stearic acid diglyceride, palmitic acid monoglyceride, palmitic acid diglyceride, oleic acid monoglyceride and oleic acid diglyceride; sucrose fatty acid esters; and mixtures of these.

[0134] Examples of cationic surfactants include at least one selected from the group consisting of alkylamine salts such as coconut amine acetate and stearylamine acetate; quaternary ammonium salts such as lauryltrimethylammonium salt, stearyltrimethylammonium salt, distearyldimethylammonium salt, alkylbenzyldimethylammonium salt, hexadecyltrimethylammonium salt, stearyltrimethylammonium salt, behenyltrimethylammonium salt, distearyldimethylammonium salt, diisotetradecyldimethylammonium salt, cetylpyridinium chloride, benzethonium chloride, benzalkonium chloride and didecyldimethylammonium chloride; and mixtures thereof.

[0135] Examples of the amphoteric surfactant include alkyl betaines such as lauryl betaine, stearyl betaine and 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine; amine oxides such as lauryl dimethylamine oxide; and at least one selected from these surfactants.

[0136] In view of excellent mixing stability with (a) solid chlorine bleach, such as sodium dichloroisocyanurate, the surfactant is preferably an anionic surfactant. In view of particularly good mixing stability with solid chlorine bleach and fineness of the formed foam, the surfactant is preferably at least one selected from sodium linear alkylbenzene sulfonate, sodium α-olefin sulfonate, sodium alkyl sulfate, and a mixture thereof.

[0137] Examples of organic polymers include at least one selected from the following: 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; methylcellulose, carboxymethylcellulose, alkali metal salts of carboxymethylcellulose, ethylcellulose, hydroxypropylcellulose, hydroxyethylcellulose, other cellulose derivatives, and mixtures thereof. Other examples include at least one synthetic polymer selected from polyvinyl alcohol, polyacrylamide, polyethylene glycol, polyacrylic acid, polymaleic acid, olefin-maleic anhydride copolymer, acrylic acid-maleic acid copolymer, acrylic acid-sulfonic acid copolymer, diallyldimethylammonium polymer, diallyldimethylammonium-acrylic acid copolymer, diallylmethylamine-maleic acid copolymer, alkali metal salts thereof, halides thereof, and mixtures thereof. A variety of organic polymers may be used in combination.

[0138] Among organic polymers, polysaccharides are preferred in view of the effect of preventing dirt from attaching again. Among polysaccharides, in view of the mixing stability with solid chlorine bleach, for example, at least one selected from the following is preferred: carrageenan, guar gum, locust bean gum, xanthan gum, and mixtures thereof, and guar gum is more preferred. In view of imparting dispersibility to the hardness components contained in water, synthetic polymers are preferred. Among synthetic polymers, for example, at least one selected from the following is preferred: polyacrylic acid, polymaleic acid, olefin-maleic anhydride copolymer, acrylic acid-maleic acid copolymer, alkali metal salts thereof, and mixtures thereof. Such synthetic polymers and alkali metal salts thereof preferably have a weighted average molecular weight of 5,000 or more and 200,000 or less, and more preferably 10,000 or more and 180,000 or less.

[0139] In order to prevent dirt from attaching again and to avoid excessive increase in water viscosity when the cleaning composition is dissolved in water, when the cleaning composition contains a polysaccharide, the amount of the polysaccharide is preferably in the range of 0.01 wt.% to 10 wt.%, more preferably 0.1 wt.% to 7 wt.%, and further more preferably 0.5 wt.% to 5 wt.%, based on the weight of the cleaning composition. In order to obtain sufficient dispersion of the hardness component, the content of the synthetic polymer in the cleaning composition is preferably in the range of 0.1 wt.% to 80 wt.%, more preferably 1 wt.% to 60 wt.%, and further more preferably 1 wt.% to 40 wt.%, based on the total weight of the cleaning composition.

[0140] The organic polymer may not be added to the cleaning composition, but may be added separately to the water-filled portion of the article to be cleaned. For example, the organic polymer may be added in advance to the water-filled portion in contact with the article to be cleaned, and then the cleaning composition may be added. In this case, the amount of the organic polymer added separately may be in the same range as when the organic polymer is added to the cleaning composition.

[0141] Examples of chelating agents include at least one selected from the following: aminocarboxylic acid derivatives, such as cyanotriacetic acid, ethylenediaminetetraacetic acid, β-alanine diacetic acid, aspartic acid diacetic acid, methylglycine diacetic acid, iminodisuccinic acid, glutamic acid diacetic acid, metal salts thereof, and hydrates thereof; hydroxyaminocarboxylic acids, such as serine diacetic acid, hydroxyiminodisuccinic acid, hydroxyethylethylenediaminetriacetic acid, dihydroxyethylglycine, metal salts thereof, and hydrates thereof; phosphoric acid carboxylic acid derivatives, such as tripolyphosphoric acid, 1-diphosphoric acid, α-methylphosphosuccinic acid, 2-phosphobutane-1,2-dicarboxylic acid, metal salts thereof, and hydrates thereof; and mixtures thereof. In view of easy availability, easy handling, and the scavenging effect on metal ions, preferably at least one chelating agent selected from aminocarboxylic acid metal salts, aminocarboxylic acid metal salt hydrates, hydroxyaminocarboxylic acid metal salts, hydrates of hydroxyaminocarboxylic acid metal salts, and mixtures thereof. A preferred example of the metal salt of the chelating agent is the sodium salt. In view of the excellent stability with solid chlorine bleach, the chelating agent is preferably sodium cyanotriacetic acid. When the cleaning composition contains a chelating agent, the chelating agent content in the cleaning composition must be higher than a predetermined amount in view of the scavenging effect on metal ions. However, even if an excessive amount of chelating agent is added, it is impossible to expect further improvement in the effect. Therefore, the amount of the chelating agent is preferably 0.1wt.% to 80wt.%, more preferably 1wt.% to 60wt.%, and further more preferably 1wt.% to 40wt.%.

[0142] Examples of pigments include Scarlet G conc., Permanent Red GY, Seikafast (registered trademark) Carmine 3870, Seikafast Yellow 2200, Seikafast Yellow 2700 (B) (trade name, Dainichiseika Color & Chemicals Mfg. Co., Ltd.), Acid Blue 9, Direct Yellow 12 (trade name, Tokyo Chemical Industry Co., Ltd.), Phthalocyanine Blue, Riboflavin (trade name, Wako Pure Chemical Industries, Ltd.) and Ultramarine Blue (trade name, Hayashi Pure Chemical Industries, Ltd.). These pigments may be added alone or in combination of two or more. The pigment content in the cleaning composition is preferably 0.1wt.% to 5wt.%.

[0143] Examples of spices that can be used include natural spices and synthetic spices. For example, spices with various smells such as mint, lime and citrus can be used. The fragrance content in the cleaning composition is preferably 0.1 wt.% to 8 wt.%.

[0144] Examples of enzymes that can be used include various enzymes that can be used for cleaning.

[0145] Examples of inorganic substances (excluding alkaline compounds) include sulfates, acetates, alkali metal chlorides, aluminum sulfates, siloxanes, clay minerals, and boron compounds. When the cleaning composition contains inorganic substances (excluding alkaline compounds), the content of inorganic substances in the cleaning composition is preferably 0.1 wt.% to 60 wt.%, more preferably 1 wt.% to 40 wt.%, and further more preferably 1 wt.% to 20 wt.%, based on the weight of the cleaning composition, because too low an inorganic substance content in the cleaning composition cannot provide the expected effect, and too high an inorganic substance content will limit the content of bleach and alkaline compounds.

[0146] Examples of sulfates include alkali metal salts of sulfuric acid, such as sodium sulfate and potassium sulfate; and alkaline earth metal salts of sulfuric acid, such as magnesium sulfate and calcium sulfate. Examples of acetates include alkali metal salts of acetic acid, such as sodium acetate and potassium acetate; and alkaline earth metal salts of acetic acid, such as magnesium acetate and calcium acetate. Examples of alkali metal chlorides include sodium chloride and potassium chloride. Examples of aluminum sulfates include potassium aluminum sulfate (sometimes also referred to as alum). Examples of clay minerals include hectorite. Examples of boron compounds include borax, boric acid, metaboric acid and boric oxide. Examples of siloxanes include dimethylpolysiloxane. These inorganic substances can be added to the cleaning composition alone or in a combination of two or more.

[0147] Preferred embodiments of the cleaning composition

[0148] In view of solubility in water, the cleaning composition of the present invention is preferably in a powder form. Preferred examples of the solid chlorine bleach in the material containing the solid chlorine bleach with a coating include sodium dichloroisocyanurate, sodium dichloroisocyanurate hydrate and potassium dichloroisocyanurate; more preferably sodium dichloroisocyanurate.

[0149] In view of good solubility in water, the coating of the material containing the solid chlorine bleach having a coating is preferably a metal salt of a carboxylic acid. The metal salt of a carboxylic acid is, for example, at least one selected from metal salts of aromatic carboxylic acids, alkali metal salts of acyclic dicarboxylic acids, alkali metal salts of acyclic monocarboxylic acids, and mixtures thereof. Metal salts of aromatic carboxylic acids are particularly preferred because they are easy to process into a coating and are readily available.

[0150] Preferred examples of metal salts of aromatic carboxylic acids are at least one selected from metal salts of benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid and p-tert-butylbenzoic acid, and mixtures thereof. Examples of metal salts include alkali metal salts such as lithium salts, sodium salts and potassium salts; and alkaline earth metal salts such as calcium salts. In view of easy availability, alkali metal salts are preferred. In view of solubility in water, sodium salts and potassium salts are more preferred. Particularly preferred examples of metal salts of aromatic carboxylic acids are at least one selected from alkali metal salts of benzoic acid, alkali metal salts of p-tert-butylbenzoic acid, and mixtures thereof. Preferred examples of metal salts of aromatic carboxylic acids are sodium benzoate and sodium p-tert-butylbenzoate.

[0151] Preferred examples of the metal salt of acyclic dicarboxylic acid are at least one selected from the metal salts of succinic acid, fumaric acid, maleic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tetradecanedioic acid, and mixtures thereof. Preferred examples of the metal salt are alkali metal salts. Considering the solubility in water, sodium salts and potassium salts are more preferred, and examples of the metal salt of acyclic dicarboxylic acid include disodium sebacate, disodium undecanedioic acid, disodium dodecanedioic acid, and disodium tetradecanedioic acid.

[0152] The example of the metal salt of acyclic monocarboxylic acid is at least one selected from the metal salts of hexanoic acid, heptanoic acid (heptanoate), octanoic acid, nonanoic acid, decanoic acid, dodecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, oleic acid, linoleic acid, linolenic acid, acrylic acid, methacrylic acid, isobutyric acid and isovaleric acid. The metal salt is preferably an alkali metal. Considering the solubility in water, it is further more preferably a sodium salt and a potassium salt. Preferred examples of the metal salt of acyclic monocarboxylic acid include sodium caproate, sodium heptanoate, sodium octanoate, sodium nonanoate, sodium decanoate, sodium dodecanoate, sodium laurate and sodium myristate.

[0153] Preferred examples of other carboxylates are metal salts of citric acid. Preferred examples of metal salts are alkali metal salts. Considering solubility in water, sodium salts and potassium salts are more preferred.

[0154] These metal salts of aromatic carboxylic acids, metal salts of acyclic dicarboxylic acids, and metal salts of acyclic monocarboxylic acids may be used alone or in combination of two or more thereof.

[0155] Preferred examples of the alkaline compound that can be used in the present invention include metal metasilicates, hydrates of metal metasilicates, and hydroxides of alkali metals. Preferred examples of metal salts are alkali metal salts, such as sodium salts and potassium salts. Preferred examples of metal metasilicates include sodium metasilicate. Preferred examples of hydrates of metal metasilicates are sodium metasilicate pentahydrate and sodium metasilicate nonahydrate.

[0156] The water that can be used in the present invention is preferably bound water. In particular, the alkaline compound having bound water is preferably sodium metasilicate pentahydrate and sodium metasilicate nonahydrate. Sodium dichloroisocyanurate hydrate can also be used as a solid chlorine bleaching agent having bound water.

[0157] Method for preparing a material containing a solid chlorine bleach having a coating

[0158] The material containing the solid chlorine bleach with a coating layer of the present invention can be prepared by a known method. For example, a compound for forming a coating layer is dissolved in a solvent, such as water or ethanol, to form a solution. The solid chlorine bleach is made to flow in a rolling granulator or a fluidized bed granulator. An aqueous solution of the compound for forming a coating layer is sprayed on the solid chlorine bleach. Thus, a coating layer can be formed on the solid chlorine bleach. Other preparation methods can also be used. The preparation method described in Patent Document 2 (PTL2) can also be used.

[0159] Method for preparing cleaning composition

[0160] The cleaning composition of the present invention can be prepared by mixing a material containing a solid chlorine bleach having a coating with the above-mentioned alkaline compound and optionally other additives. The ingredients contained in the cleaning composition can be placed in a known mixer and further packaged into a small container, such as a film, a pouch or a bottle. The ingredients contained in the cleaning composition can also be directly placed in a small container, such as a film, a pouch or a bottle, without using a mixer.

[0161] Method of using the cleaning composition

[0162] The cleaning composition of the present invention is placed in an article to be cleaned having a portion filled with water, thereby effectively cleaning or bleaching dirt on the article to be cleaned. Examples of articles to be cleaned include hard surfaces near water, which are in contact with water and easily accumulate dirt. Specific examples include kitchens, washrooms, bathrooms, toilets, etc., which are filled with water, drains, drain pipe interiors, etc., and washing tubs of washing machines, including drum-type washing machines and vertical washing machines.

[0163] The cleaning composition and cleaning method of the present invention can be used safely because the heat generated when the cleaning composition is in contact with a small amount of water is reduced. In addition, the cleaning composition of the present invention is suitable for distribution because the cleaning composition in a packaged state can suppress the expansion and rupture of the packaging container. The cleaning composition of the present invention is easy to handle because the active ingredients of the bleaching agent do not deteriorate and can be stored for a long time. In addition, the cleaning composition of the present invention has excellent cleaning and bleaching effects based on the alkalinity when dissolved in water and the solid chlorine bleach contained therein. In addition, when the object to be cleaned is metal, the cleaning composition of the present invention can also suppress the solid chlorine bleach from corroding the metal.

[0164] When the cleaning composition and cleaning method of the present invention are used for the washing machine drum of a washing machine, the cleaning composition is placed in the water accumulated in advance by the washing machine drum and the washing machine is operated, thereby the mold and biofilm inside or behind the washing machine drum can be effectively removed. When used in a drum-type washing machine, the cleaning composition can be placed in the washing machine drum, and the cleaning mode provided by the washing machine, such as the drum cleaning program, is cleaned. Cleaning the washing machine drum can not only remove the mold pollution, biofilm, soap scum and other dirts adhering to the washing machine drum, but also the washing machine drum can become clean inside, thereby reducing the odor transmission from the washing machine drum to the clothes. Therefore, the damp odor of the clothes dried by the washing machine with a drying function, for example, can be reduced.

[0165] When used to clean a drain pipe, a cleaning composition can be added from the drain outlet, and then water can be injected into the drain pipe to clean the inside of the drain pipe. The cleaning composition pre-dissolved in water can be poured into the drain pipe, or if water has accumulated in the drain pipe, the cleaning composition can be simply poured into it for cleaning. In addition, the cleaning composition of the present invention can also be used in areas where there is usually no accumulation of water, as long as it is an area that can be supplied by a combination of the cleaning composition and water. Examples include drain outlets, bathtubs, and kitchen sinks in bathrooms, etc.

[0166] In order to effectively exert the effect of the cleaning composition of the present invention, the concentration of the cleaning composition in the aqueous solution after supply is preferably in the range of 0.01 g / L to 100 g / L, more preferably 0.1 g / L to 50 g / L, and further preferably 1 g / L to 25 g / L. The higher the concentration of the cleaning composition, the easier it is to achieve a cleaning effect. However, adding an excessive amount of the cleaning composition does not expect a further improvement in the cleaning effect.

[0167] In order for the cleaning composition of the present invention to exert bleaching and cleaning effects on the cleaned items, the effective chlorine concentration in the aqueous solution after the cleaning composition is added to water is preferably 100 ppm or higher, more preferably 500 ppm or higher, and further preferably 1000 ppm or higher.

[0168] Regarding the method of using the cleaning composition, if the article to be cleaned has accumulated water, such as a water-filled part of a toilet or drain, the cleaning composition can be directly thrown into the water. If the article to be cleaned is designed to freely accommodate water therein, such as a sink, a bathtub or a washing machine, the cleaning composition can be added after the article is filled with water, or the water can be added after the cleaning composition is placed. That is, the article to be cleaned can be cleaned by the following steps: dissolving the cleaning composition in water and contacting the aqueous solution of the cleaning composition with the article to be cleaned. The cleaning method of the present invention can be carried out by the following steps: components that may be contained in the cleaning composition, such as a material containing a solid chlorine bleach with a coating and an alkaline compound and optional other additives, are added separately to water, and each component is dissolved in water; and the water in which the components are dissolved is contacted with the article to be cleaned.

[0169] Moisture content of materials containing solid chlorine bleach

[0170] The water content of the material containing the solid chlorine bleach with a coating can be measured, for example, by the following method. A predetermined amount of the material containing the solid chlorine bleach with a coating is placed on an enameled baking tray, placed in a heating furnace set at 110°C, and heated and dried until a constant weight is reached to measure the weight loss. Using the weight loss, the water content of the solid chlorine bleach with a coating can be calculated according to Formula 4. Free water evaporates when heated and dried at a temperature close to the boiling point of water under normal pressure. Therefore, for free water, the water content can be measured by heating and drying at a relatively low temperature of about 100°C.

[0171] Water content of basic compounds

[0172] For example, taking the hydrate of metal silicate as an example, the water content of the alkaline compound can be determined by the following method. Examples of hydrates of metal silicate include compounds such as sodium metasilicate pentahydrate and sodium metasilicate nonahydrate. The water molecules of these compounds exist in the form of being added to sodium metasilicate, such as sodium metasilicate pentahydrate and sodium metasilicate nonahydrate, and can be regarded as bound water. The molecular weight of sodium metasilicate is 122.06. The molecular weight of sodium metasilicate pentahydrate is 212.14. The molecular weight of water molecules (pentahydrate) in sodium metasilicate pentahydrate is 90.08. The water content of sodium metasilicate pentahydrate is calculated to be 42.46wt.% by 90.08 / 212.14×100. Similarly, the water content of sodium metasilicate nonahydrate is calculated to be 57.06wt.%.

[0173] When the water content is unknown, it can be determined by, for example, the following method. Perform TG-DTA analysis on basic compounds. For example, place the sample in an aluminum sample pan, heat it at a predetermined heating rate of 5°C / min, introduce nitrogen at a flow rate of 200 ml / min to create a nitrogen environment, and raise the temperature to about 300°C. The water content can be calculated according to Formula 4, using the weight loss calculated for aluminum oxide as a reference. For bound water, it may be necessary to heat and dry at a relatively high temperature, because the water in the compound cannot be removed if the temperature is not heated above the boiling point of water.

[0174] Compounds containing free water can also be measured using TG-DTA. The measurement conditions of TG-DTA can be appropriately set according to the properties of the compound to be measured. The water content of the cleaning composition can be measured by directly performing TG-DTA analysis on the cleaning composition.

[0175] PTL 2 (WO2017 / 183726) and its corresponding US2019 / 0153363 are incorporated herein by reference in their entirety.

[0176] Example

[0177] The present invention is specifically described by reference to examples and comparative examples. However, the present invention is not limited to these examples. The starting materials and experimental equipment used in the examples and comparative examples are as follows.

[0178] Starting Materials

[0179] -Sodium dichloroisocyanurate: produced by Shikoku Chemicals Corporation, trade name "Neochlor 60G" (actual effective chlorine content: 63.0%, water content: 1.40wt.%)

[0180] -Sodium benzoate: Reagent (manufactured by Fujifilm Wako Pure Chemical Corporation)

[0181] -Decanic acid: Reagent (manufactured by Fujifilm Wako Pure Chemical Corporation)

[0182] -Sodium hydroxide: Reagent (produced by Fujifilm Wako Pure Chemical Corporation)

[0183] -Sodium decanoate aqueous solution: disperse decanoic acid in distilled water, add an equal amount of sodium hydroxide, and stir to obtain a sodium decanoate aqueous solution (sodium decanoate concentration: 20 wt.%)

[0184] - Sebacic acid: Reagent (manufactured by Fujifilm Wako Pure Chemical Corporation)

[0185] - Disodium sebacate aqueous solution: Dissolve sebacic acid in distilled water, add an equal amount of sodium hydroxide, and stir to obtain a disodium sebacate aqueous solution (disodium sebacate concentration: 20 wt.%)

[0186] -Sodium lauryl sulfate: trade name "Emar 10PT", manufactured by Kao Corporation

[0187] -Sodium metasilicate (anhydrous): reagent (manufactured by Sigma-Aldrich, water content: 0.00 wt.% or less)

[0188] -Sodium metasilicate pentahydrate: Reagent (manufactured by Sigma-Aldrich)

[0189] -Sodium metasilicate nonahydrate: Reagent (produced by Fujifilm Wako Pure Chemical Corporation)

[0190] - Sodium diphosphate decahydrate: Reagent (manufactured by Fujifilm Wako Pure Chemical Corporation)

[0191] - Ethylenediaminetetraacetic acid tetrasodium dihydrate: Reagent (Dojindo Laboratories)

[0192] - Trisodium citrate dihydrate: Reagent (manufactured by Fujifilm Wako Pure Chemical Corporation)

[0193] Material

[0194] Aluminum Laminated Film

[0195] -Material composition (μm): PET12 / AL7 / CPP50

[0196] instrument:

[0197] -Vibrating screen:

[0198] AS200 Control, manufactured by Retsch

[0199] - Tumble granulator: DPZ-1, manufactured by As One Corporation - pH meter: F-51, manufactured by Horiba, Ltd.

[0200] -TG-DTA: STA7200RV, manufactured by Hitachi High-Tech Science Corporation

[0201] - Drum type washing machine: NA-VG740L, manufactured by Panasonic Corporation (1) Preparation of a material containing a solid chlorine bleach having a coating

[0202] -Material containing solid chlorine bleach having a coating 1

[0203] As a compound for forming a coating layer, sodium benzoate was dissolved in water to prepare a 30 wt.% sodium benzoate coating aqueous solution. Sodium dichloroisocyanurate powder was put into a rolling granulator and heated to 60° C. while rotating. The coating aqueous solution was sprayed on the sodium dichloroisocyanurate flowing in the rolling granulator. When a predetermined amount of coating layer was formed, the spraying was stopped, thereby obtaining a material containing a solid chlorine bleach having a coating layer 1. The material containing a solid chlorine bleach having a coating layer 1 had an effective chlorine content of 44.8%, a coating percentage of 26.0 wt.%, a water content of 2.90 wt.%, and an average particle size of 855 μm.

[0204] -Material containing solid chlorine bleach having a coating 2

[0205] As a compound for forming a coating layer, a 20 wt.% sodium caprate aqueous solution was prepared and used as a coating aqueous solution. A material containing a solid chlorine bleach having a coating layer 2 was prepared in the same manner as the material containing a solid chlorine bleach having a coating layer 1, except that sodium caprate was used. The material containing a solid chlorine bleach having a coating layer 2 had an effective chlorine content of 47.0%, a coating percentage of 19.3 wt.%, a water content of 5.59 wt.%, and an average particle size of 1474 μm.

[0206] -Material containing solid chlorine bleach having coating 3

[0207] As a compound for forming a coating layer, a 20 wt.% disodium sebacate aqueous solution was prepared and used as a coating aqueous solution. A material containing solid chlorine bleach having coating layer 3 was prepared in the same manner as the material containing solid chlorine bleach having coating layer 1, except that disodium sebacate was used. The material containing solid chlorine bleach having coating layer 3 had an effective chlorine content of 44.7%, a coating percentage of 25.5 wt.%, and a water content of 2.98 wt.%. The average particle size was 680 μm.

[0208] -Material containing solid chlorine bleach having a coating 4

[0209] As a compound for forming a coating, sodium lauryl sulfate was dissolved in water to prepare a 20 wt.% sodium lauryl sulfate coating aqueous solution. A material containing a solid chlorine bleach having a coating 4 was prepared in the same manner as the material containing a solid chlorine bleach having a coating 1, except that sodium lauryl sulfate was used. The material containing a solid chlorine bleach having a coating 4 had an effective chlorine content of 46.9%, a percentage of a coating of 23.0 wt.%, and a water content of 1.87 wt.%. The average particle size was 1247 μm.

[0210] (2) Water content measurement

[0211] Moisture content of materials containing coated solid chlorine bleach

[0212] The moisture content of the material containing the solid chlorine bleach with a coating is measured by the following method. A predetermined amount of the material containing the solid chlorine bleach with a coating is placed in an enameled baking tray and dried in an oven heated at 110° C. for 1 hour. After confirming that constant weight is achieved, the weight loss is measured. Using the weight loss, the moisture content is calculated according to Formula 4.

[0213] Water content of basic compounds

[0214] The water content of the alkaline compound is measured by the following method. Examples of metal silicates include compounds such as sodium metasilicate pentahydrate and sodium metasilicate nonahydrate. Water molecules in such compounds are added to sodium metasilicate in the form of, for example, pentahydrate and nonahydrate, and can be considered as bound water.

[0215] For example, sodium metasilicate has a molecular weight of 122.06, sodium metasilicate pentahydrate has a molecular weight of 212.14, and the molecular weight of the water molecule (pentahydrate) in sodium metasilicate pentahydrate is 90.08.

[0216] The water content of sodium metasilicate pentahydrate is calculated to be 42.4 wt.% by 90.08 / 212.14×100.

[0217] Therefore, the water content from sodium metasilicate pentahydrate in the cleaning composition can be calculated by multiplying the water content of sodium metasilicate pentahydrate by the content of sodium metasilicate pentahydrate in the cleaning composition. For example, when the cleaning composition contains 50.0wt.% of sodium metasilicate pentahydrate, the water content from sodium metasilicate pentahydrate in the cleaning composition is calculated to be 21.2wt.%.

[0218] Similarly, the water content of sodium metasilicate nonahydrate is calculated to be 57.06wt.%. The amount of water from sodium metasilicate nonahydrate in the cleaning composition can be calculated by multiplying the water content of sodium metasilicate nonahydrate by the content of sodium metasilicate nonahydrate in the cleaning composition. For example, when the cleaning composition contains 50.0wt.% of sodium metasilicate nonahydrate, the water content from sodium metasilicate nonahydrate in the cleaning composition is calculated to be 28.5wt.%.

[0219] When the cleaning composition contains multiple basic compounds, the sum of the water contents of these compounds is the water content of the basic compound. When the hydrate content is unknown, the basic compound is placed on an aluminum sample pan and the weight loss is measured by TG-DTA when the temperature is raised to 300°C at a heating rate of 5°C / min and a nitrogen purge gas flow rate of 200 ml / min. The water content is calculated according to Formula 4. Alumina is used as a reference.

[0220] Sodium metasilicate pentahydrate has a water content of 42.46 wt.%. Sodium metasilicate nonahydrate has a water content of 57.06 wt.%. Sodium diphosphate decahydrate has a water content of 40.39 wt.%.

[0221] The water content of other compounds is measured in the same manner as the method for measuring the water content of the basic compound. In addition, when the compound decomposes at a temperature of 300° C. or below, the measurement conditions are appropriately set according to the properties of the compound, for example, the measurement is performed after lowering the heating temperature.

[0222] (3) Evaluation method

[0223] The cleaning composition obtained above was packaged in an aluminum laminate film to obtain a packaged cleaning composition.

[0224] The average particle size of the powder is measured by the method described in the "Powder" section of this specification. The raw material powders used in the present invention all have an average particle size in the range of 200 to 1000 μm.

[0225] Heat generation test

[0226] 6.8 g of the powdered cleaning composition having the formulation shown in Tables 1 to 8 below were placed in 50 ml beakers respectively. A thermometer was placed in each beaker, 5 ml of distilled water (room temperature) was added, and the temperature was recorded every 1 minute until 20 minutes had passed. The highest temperature measured within 20 minutes was taken as the heat generation temperature T 5ml .

[0227] The results are shown in Tables 1 to 8 below.

[0228] Storage stability test; Changes in effective chlorine retention over time

[0229] 30 g of a powdered cleaning composition having a formula shown in Tables 1 to 8 was placed in an aluminum laminate film and sealed by heat sealing to obtain a cleaning composition packaged in a bag using an aluminum laminate film. The cleaning composition was placed in an oven set at 50° C. and stored for 4 weeks. After the first four weeks, each cleaning composition was taken out of the aluminum laminate film, mixed and ground to uniformity. The available chlorine content was determined by iodine titration. The ratio of the available chlorine content of the cleaning composition after the storage stability test to the available chlorine content of the cleaning composition before the storage stability test was calculated as the available chlorine retention rate. Tables 1 to 8 show the results. When the aluminum laminate film sealing the packaging of each cleaning composition swelled and ruptured within less than 4 weeks after being placed in the oven, the test was terminated immediately, and the available chlorine content when the bag was ruptured was recorded. When the packaging container is a bag, rupture may refer to bag rupture.

[0230] Storage stability test; packaging container expansion evaluation

[0231] 30g of the powdered cleaning composition with the formula shown in Tables 1 to 8 is placed in an aluminum laminate film, sealed by heat sealing, and packaged in an aluminum laminate film in the same manner as the above-mentioned measurement of effective chlorine retention rate. The packaging container containing the cleaning composition is placed in an oven set to 50°C and stored for 4 weeks. After the start of four weeks, the appearance of each packaging container is visually inspected. When the packaging container expands and breaks (bag breaks) or when the bag does not break but obvious expansion is confirmed, it is rated as "×". When it is observed that the packaging container expands slightly, it is rated as "△". When the packaging container is hardly observed to expand, it is rated as "○".

[0232] pH Measurement

[0233] The powdered cleaning compositions having the formulations shown in Tables 1 to 8 were dissolved in distilled water to prepare 1 wt.% aqueous solutions, and the temperature of each aqueous solution was adjusted to 25° C. About 50 ml of each aqueous solution was used after stirring to measure the pH value with a pH meter. The pH meter was calibrated at three points using standard solutions of pH 4, pH 7, and pH 9 immediately before measurement.

[0234] Cleaning Test 1: Cleaning a Soiled Cloth Using a Cleaning Composition

[0235] A powdered cleaning composition having a formulation shown in Table 8 was dissolved in distilled water to prepare a 0.02 wt. % cleaning aqueous solution. The pH value and effective chlorine concentration (mg / L) of each cleaning aqueous solution were measured.

[0236] Further, 800ml of the cleaning aqueous solution was charged into a 1L beaker, and half of the cloth area of ​​a 5cm×5cm black tea dyed cotton cloth (STC EMPA 167, produced by Nippon Shizai Co., Ltd.) was immersed in the cleaning aqueous solution and left to stand for 30 minutes at 20°C. After 30 minutes, the cotton cloth was taken out and dried at room temperature. A whiteness meter (digital whiteness meter TC-6D, produced by Tokyo Denshoku) was used to measure the whiteness of the area immersed in the cleaning aqueous solution and the whiteness of the unimmersed area. The whiteness of the area immersed in the cleaning aqueous solution reflects the bleaching effect of the cleaning aqueous solution, while the whiteness of the unimmersed area reflects the color of the cotton cloth before cleaning. Therefore, it can be considered that the greater the difference in whiteness between these areas, the higher the bleaching effect of the cleaning aqueous solution. Note that the higher the whiteness value means that the color of the target object is closer to white. For whiteness, JIS Z 8715 (Japanese Industrial Standards, "Color Specifications - Whiteness") and JIS Z 8722 (Japanese Industrial Standards, "Color Measurement Methods - Reflective and Transmissive Objects") may be referred to. The cotton cloth used in this test may also be appropriately selected from other cotton cloths that differ from the above-mentioned cloths in dyeing method or material. When there is no whiteness meter, whiteness may be evaluated visually.

[0237] Cleaning Test 2: Cleaning of Washing Machine Drum Slices Using Cleaning Composition

[0238] The powdered cleaning composition with the formula shown in Table 8 was dissolved in distilled water to prepare a 0.8wt.% cleaning aqueous solution. 105mL of the cleaning aqueous solution was added to a 125L container made of polypropylene (PP) resin. The resin washing drum of a common washing machine (domestic fully automatic washing machine NA-F42S1, Matsushita Electric Industrial Co., Ltd.) that has accumulated black mold and dirt in actual use was cut into a square of 5cm×5cm and used as a test piece. The test piece was immersed in a 25°C cleaning aqueous solution for 3 hours, and the condition of the test piece after cleaning was visually evaluated. When most of the dirt was removed, the cleaning composition was rated as ◎. When about half of the dirt was removed, the cleaning composition was rated as ○. When most of the dirt was still not removed or there was no dirt removal at all, the cleaning composition was rated as ×.

[0239] Washing machine usage test

[0240] The cleaning composition packaged with aluminum laminate film was tested in a washing machine. The aluminum laminate film containing 200 g of the cleaning composition was opened, and the entire 200 g of the cleaning composition was placed in the washing drum of a drum washing machine (Panasonic, NA-VG740L). The washing drum was cleaned by selecting the "leave it to us" program or the "drum cleaning course" on the washing machine panel. The inside of the washing drum during cleaning was observed through the doors and windows, and the sewage after cleaning or the aqueous solution in the washing drum during cleaning was collected and the effective chlorine concentration and pH value were measured.

[0241] In the present specification, the wording "suppressing heat generation" means that when water is added to a predetermined amount of the cleaning composition, the maximum temperature reached by the temperature rise due to heat generation is lower than a reference temperature.

[0242] The phrase "inhibiting expansion and rupture of a packaging container" means that when the cleaning composition is sealed in a predetermined packaging container, the volume increase of the packaging container is less than that of a comparative composition, or the time taken for a portion of the packaging container to rupture is greater than that of the comparative composition, or the degree of rupture of the packaging container is less than that of the comparative composition.

[0243] The phrase "chlorine bleach remains stable" means that after the cleaning composition is stored for a certain period of time under predetermined conditions, the effective chlorine retention rate of chlorine bleach as an active ingredient is higher than that of a comparative composition.

[0244] In the comparative examples, a trend of increasing heat generation as the water content of the cleaning composition decreases was observed. Therefore, in the examples, cleaning compositions having the same effective chlorine content were prepared and compared with the cleaning compositions in the comparative examples, which did not contain a material containing a solid chlorine bleach having a coating, and whose types of compounds used as constituents were the same as those in the examples, differing only in the content ratio. If the maximum temperature reached due to the heating of the cleaning composition in the examples (wherein the water content of the cleaning composition is almost equal to or lower than that of the corresponding cleaning composition in the comparative examples) is almost equal to or lower than that of the corresponding cleaning composition in the comparative examples, then the cleaning composition in the examples is considered to "inhibit heat generation".

[0245] In the comparative examples, as the water content of the cleaning composition increases, the expansion and rupture of the packaging container tend to increase. Therefore, in the examples where the effective chlorine content of the cleaning composition is the same and the water content of the cleaning composition is almost equal to or higher than the cleaning composition in the comparative example, if the expansion or rupture of the packaging container (bag rupture) is small, or the time required for the expansion or rupture to occur is long, then the cleaning composition of the example can be considered to "inhibit the expansion and rupture of the packaging container".

[0246] Furthermore, in the comparative examples, it was observed that the effective chlorine retention rate of the cleaning composition tended to decrease as the water content of the cleaning composition increased. Therefore, in embodiments where the water content of the cleaning composition is almost equal to or greater than that of the cleaning composition in the comparative examples, if the decrease in the effective chlorine retention rate of the cleaning composition is suppressed, the cleaning composition can be considered to have a "high effective chlorine retention rate".

[0247] (4) Preparation and evaluation of cleaning compositions

[0248] Examples 1 to 3 and Comparative Examples 1 to 3

[0249] The solid chlorine bleach or sodium dichloroisocyanurate having coating 1 and sodium metasilicate (anhydrous) and / or sodium metasilicate pentahydrate were mixed according to the formula shown in Table 1 to prepare a cleaning composition having an effective chlorine content of 13.5%. These cleaning compositions were individually packaged with aluminum laminate films. The water content, effective chlorine content, pH value of the aqueous solution, heat generation temperature and storage stability test results of each cleaning composition are shown in Table 1.

[0250]

[0251] The material containing solid chlorine bleach with coating 1 has a water content of 2.90 wt. %. Therefore, when the cleaning composition contains 30.0 wt. % of the material containing solid chlorine bleach with coating 1, the water content from the solid chlorine bleach in the cleaning composition is 0.870 wt. %.

[0252] In addition, the water content of sodium metasilicate pentahydrate is 42.5wt.%. Therefore, when the cleaning composition contains 35.0wt.% (Example 2) or 70.0wt.% (Example 3) of sodium metasilicate pentahydrate, the cleaning compositions (Examples 2 and 3) have a water content of 14.9wt.% and 29.7wt.% from the alkaline compounds in the cleaning composition, respectively.

[0253] The water content of the cleaning composition obtained in Example 1 containing only sodium metasilicate (anhydrous) as the alkaline compound is equal to the water content from the solid chlorine bleach. The water content of the cleaning compositions containing sodium metasilicate pentahydrate in Examples 2 and 3 is equal to the sum of the water content from the material containing the solid chlorine bleach with a coating and the water content from the alkaline compound. The water content of the cleaning compositions in Examples 2 and 3 is 15.8 wt.% and 30.6 wt.%, respectively. The water content of the cleaning compositions in Comparative Examples 1 to 3 can also be calculated in the same way.

[0254] As shown in Table 1, in Examples 1 to 3, as the water content of the cleaning composition increases, the heat generation temperature T 5ml The results showed that in all the examples, the effective chlorine retention rate was reduced and the expansion of the packaging container was suppressed.

[0255] On the other hand, in Comparative Examples 1 to 3, it was also observed that the heat generation temperature decreased as the water content in the cleaning composition increased. 5ml In addition, in Comparative Examples 2 and 3, although the heat generation tended to be suppressed as the water content of the cleaning composition increased, a decrease in the effective chlorine retention rate and a tendency for the packaging container to swell were observed.

[0256] In addition, Example 1 is compared with Comparative Example 1, Example 2 is compared with Comparative Example 2, and Example 3 is compared with Comparative Example 3, wherein in each pair, the water content of the cleaning composition is almost equal, clearly indicating that there is a significant difference between the composition of the Example and the composition of the Comparative Example in the effect of suppressing heat generation and suppressing expansion of the packaging container. Therefore, by comparing Examples 1 to 3 with Comparative Examples 1 to 3, it can be confirmed that even if the effective chlorine content of the cleaning composition is equal, the expansion or rupture of the packaging container can be suppressed in Examples 1 to 3, while suppressing the heat generation that occurs when water is added to the cleaning composition, and the cleaning compositions of Examples 1 to 3 have a higher effective chlorine retention rate.

[0257] In Comparative Examples 1 to 3, as the water content of the cleaning composition increases, the expansion or rupture of the packaging container and the reduction in the effective chlorine retention rate become more significant. On the other hand, in Examples 1 to 3, the water content of the cleaning composition is higher than that of Comparative Example 1, and the expansion or rupture of the packaging container and the reduction in the effective chlorine retention rate are equal or suppressed. These results demonstrate the effectiveness of Examples 1 to 3.

[0258] Similarly, in Comparative Examples 1 to 3, as the water content of the cleaning composition decreased, the increase in heat generation temperature became more significant, while in Examples 2 and 3, the water content of the cleaning composition was equal to or lower than that of Comparative Example 3, and the heat generation temperature was equal to or suppressed compared with Comparative Example 3. In Example 1, the heat generation temperature was also significantly suppressed compared with Comparative Example 1, which had the same level of water content as that of Example 1. These results demonstrate the effectiveness of Examples 1 to 3.

[0259] Examples 4 to 7 and Comparative Examples 4 to 7

[0260] The solid chlorine bleach or sodium dichloroisocyanurate having coating 1 and sodium metasilicate (anhydrous) and / or sodium metasilicate pentahydrate were mixed according to the formula shown in Table 2 to prepare a cleaning composition having an effective chlorine content of 19.1%. These cleaning compositions were packaged in aluminum laminated films. The water content, effective chlorine content, pH value of each aqueous solution, heat generation temperature and storage stability test results of each cleaning composition are shown in Table 2. The water content was calculated using the same method as in Examples 1 to 3.

[0261]

[0262] As shown in Table 2, in Examples 4 to 7, as the water content of the cleaning composition increases, the heat generation temperature T 5ml In addition, the results show that in all the examples, the effective chlorine retention rate is reduced and the expansion of the packaging container is suppressed.

[0263] On the other hand, although it is also observed in Comparative Examples 4 to 7 that the exothermic temperature tends to decrease with the increase in the water content in the cleaning composition, the exothermic temperature T 5ml In addition, high heat generation was observed. The heat generation temperature T 5ml All exceeded 102° C. In addition, in Comparative Examples 4 to 7, as the water content of the cleaning composition increased, the effective chlorine retention rate decreased, and a tendency of swelling or rupture of the packaging container was observed. Therefore, compared with Comparative Examples 4 to 7, the results of Examples 4 to 7 confirmed that even when the effective chlorine content of the cleaning composition was the same, it was possible to suppress swelling or rupture of the packaging container, suppress heat generation, and achieve a high effective chlorine retention rate.

[0264] In Comparative Examples 4 to 7, as the water content of the cleaning composition increased, the swelling or rupture of the packaging container and the decrease in the effective chlorine retention rate became more obvious, while in Examples 4 to 7, in which the water content of the cleaning composition was higher than that in Comparative Example 4, the swelling or rupture of the packaging container and the decrease in the effective chlorine retention rate were equal or suppressed. This proves the effectiveness of Examples 4 to 7.

[0265] Similarly, in Comparative Examples 4 to 7, as the water content of the cleaning composition decreased, the increase in heat generation temperature became more obvious, while in Examples 4 to 7, in which the water content of the cleaning composition was lower than that of Comparative Example 7, the heat generation temperature was suppressed compared with Comparative Example 7. This proves the effectiveness of Examples 4 to 7.

[0266] Examples 8 to 11 and Comparative Examples 8 to 11

[0267] The solid chlorine bleach or sodium dichloroisocyanurate having coating 1 and sodium metasilicate (anhydrous) and / or sodium metasilicate pentahydrate were mixed according to the formula shown in Table 3 to prepare a cleaning composition having an effective chlorine content of 22.5%. The water content, effective chlorine content, pH value of each aqueous solution, heat generation temperature and storage stability test results of each cleaning composition are shown in Table 3.

[0268] The water content was calculated using the same method as in Examples 1 to 3.

[0269]

[0270] As shown in Table 3, in Examples 8 to 11, as the water content of the cleaning composition increases, the heat generation temperature T 5ml In addition, the results show that in all the examples, the reduction of the effective chlorine retention rate and the expansion of the packaging container are suppressed.

[0271] On the other hand, although it is also observed in Comparative Examples 8 to 11 that the heat generation temperature tends to decrease with the increase in the water content of the cleaning composition, the heat generation temperature T 5ml All exceeded 95° C. In addition, in Comparative Examples 9 to 11, as the water content of the cleaning composition increased, the effective chlorine retention rate decreased, and a tendency of swelling or rupture of the packaging container was observed. Therefore, compared with Comparative Examples 8 to 11, the results confirmed that even when the effective chlorine content was the same, the cleaning compositions of Examples 8 to 11 suppressed swelling or rupture of the packaging container, suppressed heat generation, and had a high effective chlorine retention rate.

[0272] In Comparative Examples 8 to 11, as the water content of the cleaning composition increased, the expansion or rupture of the packaging container and the decrease in the effective chlorine retention rate became more obvious, while in Examples 8 to 11, in which the water content of the cleaning composition was higher than that of Comparative Example 8, the expansion or rupture of the packaging container and the decrease in the effective chlorine retention rate were suppressed the same or more than that of Comparative Example 8. Even compared with Comparative Example 9, in Examples 9 to 11, in which the water content of the cleaning composition was higher than that of Comparative Example 9, the expansion or rupture of the packaging container and the decrease in the effective chlorine retention rate were better suppressed. This proves the effectiveness of Examples 8 to 11.

[0273] Similarly, in Comparative Examples 8 to 11, as the water content of the cleaning composition decreases, the increase in heat generation temperature becomes more obvious, while in Examples 8 to 11, in which the water content of the cleaning composition is lower than that of Comparative Example 11, the heat generation temperature is lower than that of Comparative Example 11. This proves the effectiveness of Examples 8 to 11.

[0274] Example 12 and Comparative Example 12

[0275] The solid chlorine bleach or sodium dichloroisocyanurate having coating 1 and sodium metasilicate (anhydrous) and sodium metasilicate nonahydrate were mixed according to the formula shown in Table 4 to prepare a cleaning composition having an effective chlorine content of 19.1% and a water content of 25.6 wt.%. These cleaning compositions were packaged in aluminum laminated films. The water content, effective chlorine content, pH value of each aqueous solution, heat generation temperature and storage stability test results of each cleaning composition are shown in Table 4. The water content was calculated using the same method as in Examples 1 to 3.

[0276]

[0277] As shown in Table 4, Example 12 is compared with Comparative Example 12, in which the effective chlorine content and water content of the cleaning composition are equivalent, and it is shown that in Example 12, the heat generation temperature T 5ml The higher effective chlorine retention rate was maintained, and the packaging container did not expand, while a higher heat generation temperature T was observed in Comparative Example 12. 5ml , the effective chlorine retention rate is significantly reduced, and the packaging container swells and ruptures. This proves the effectiveness of Example 12.

[0278] Examples 13 to 15 and Comparative Examples 13 to 15

[0279] Solid chlorine bleach or sodium dichloroisocyanurate with coating 1 and sodium metasilicate (anhydrous), sodium metasilicate pentahydrate, sodium metasilicate nonahydrate, sodium diphosphate decahydrate, and other additives tetrasodium ethylenediaminetetraacetic acid dihydrate and trisodium citrate dihydrate are mixed according to the formula shown in Table 5 to prepare a cleaning composition with an effective chlorine content of 19.1%. These cleaning compositions are packaged in aluminum laminated film. The water content, effective chlorine content, pH value of each aqueous solution, heat generation temperature and storage stability test results of each cleaning composition are shown in Table 5. The water content is calculated using the same method as in Examples 1 to 3. The water content of tetrasodium ethylenediaminetetraacetic acid dihydrate is 8.66wt.%, and the water content of trisodium citrate dihydrate is 12.3wt.%.

[0280]

[0281] As shown in Table 5, in Examples 13 to 15, the heat generation temperature T 5ml The higher effective chlorine retention rate was maintained, and no expansion of the packaging container occurred. In Comparative Examples 13 to 15, a higher heat generation temperature T 5ml , and in Comparative Example 15, the effective chlorine retention rate was significantly decreased, and swelling or rupture of the packaging container occurred.

[0282] Examples 16 to 18

[0283] One of the solid chlorine bleaching agents having coatings 2 to 4, sodium metasilicate (anhydrous) and sodium metasilicate pentahydrate were mixed according to the formula shown in Table 6 to prepare cleaning compositions having an alkaline compound (excluding hydration water) content of 48.5%. These cleaning compositions were packaged in aluminum laminated films. The water content, effective chlorine content, pH value of each aqueous solution, heat generation temperature and storage stability test results of each cleaning composition are shown in Table 6. The water content was calculated using the same method as in Examples 1 to 3.

[0284] Table 6

[0285]

[0286] As shown in Table 6, the cleaning compositions of Examples 16 to 18 all suppressed the heat generation temperature T 5ml A high effective chlorine retention rate is maintained, and no expansion of the packaging container occurs.

[0287] Comparative Example 16

[0288] The solid chlorine bleach having coating 1, sodium metasilicate nonahydrate and distilled water were mixed according to the formula shown in Table 7 to prepare a coating composition having an effective chlorine content of 19.1%. These cleaning compositions were packaged in aluminum laminated films. The water content, effective chlorine content, pH value of each aqueous solution, heat generation temperature and storage stability test results of each cleaning composition are shown in Table 7. Table 7 also shows the results of Example 12. The water content was calculated using the same method as in Examples 1 to 3.

[0289] Table 7

[0290]

[0291] *8: Bag rupture at 6 hours; retention rate after 6 hours.

[0292] As shown in Table 7, the comparison between Example 12 and Comparative Example 16 shows that since the water content of the cleaning composition in Comparative Example 16 is as high as 40.3 wt.%, the effective chlorine retention rate is significantly reduced, and the packaging container swells or ruptures.

[0293] Comparative Example 17

[0294] The solid chlorine bleach with coating 1, sodium metasilicate (anhydrous) and sodium metasilicate pentahydrate and tetrasodium ethylenediaminetetraacetic acid dihydrate as other additives were mixed according to the formula shown in Table 8 to prepare a cleaning composition with an effective chlorine content of 2.8%. The cleaning composition was packaged in an aluminum laminate film. The water content, effective chlorine content, pH value of each aqueous solution, heat generation temperature and storage stability test results of each cleaning composition are shown in Table 8. Table 8 also includes the results of Examples 1, 5 and 13. The water content was calculated using the same method as in Examples 1 to 3.

[0295]

[0296] As shown in the results of Table 8, the results of Cleaning Tests 1 and 2 show that the cleaning composition of Comparative Example 17 exhibits a low cleaning effect compared to the cleaning compositions of Examples 1, 5 and 13 because the effective chlorine content of the cleaning composition of Comparative Example 17 is as low as 2.8%.

[0297] Embodiment 19

[0298] The aluminum laminate film containing 200 g of the cleaning composition of Example 5 as a cleaning agent was opened. The entire 200 g cleaning composition was placed in the washing drum of a drum-type washing machine (Panasonic, NA-VG740L). The washing drum was cleaned by selecting the "Leave it to us" program on the washing machine panel. After cleaning, the aqueous solution flowing out of the washing machine drain pipe was collected, and the effective chlorine concentration and pH value were measured. Water was poured into the washing drum, and the cleaning composition was confirmed to be dissolved in the drum through the door and window of the washing machine without any abnormality.

[0299] As a result, the "Leave it to us" program was selected, and the first drainage was performed about 20 minutes after the "Leave it to us" program started. During the drainage process, wastewater was collected from the drain pipe of the washing machine as a sample, and the effective chlorine concentration and pH value were measured. The effective chlorine concentration was 3875 mg / L and the pH value was 12.49. Therefore, the sample had sufficient effective chlorine concentration and alkalinity. The results show that the cleaning composition is expected to provide an efficient cleaning effect on the fluff filter and drainage channel in the washing drum and the inside of the drain pipe. In addition, during the first drainage, the wastewater was collected from the drain pipe. The amount of wastewater collected was 9L. Therefore, the concentration of the detergent is considered to be 23g / L.

[0300] Embodiment 20

[0301] The aluminum laminate film containing 200 g of the cleaning composition of Example 5 as a cleaning agent was opened, and all 200 g of the cleaning composition was placed in the washing drum of a drum-type washing machine (Panasonic, NA-VG740L). The washing drum was cleaned by selecting the "drum cleaning program" (water temperature: about 30°C) on the washing machine panel. Five minutes after the drum cleaning started, the cleaning was temporarily stopped, and the cleaning aqueous solution in the drum was sampled to measure the effective chlorine concentration and pH value. After the drum cleaning started, it was confirmed through the door and window of the washing machine that the cleaning composition was dissolved in the drum without any abnormality. The drum cleaning program lasted for about 150 minutes.

[0302] As a result, 5 minutes after the drum cleaning started, the effective chlorine concentration of the aqueous solution in the washing drum was 1939 mg / L and the pH value was 11.83, thus having sufficient effective chlorine concentration and high alkalinity. The results show that the cleaning composition is expected to provide an efficient cleaning effect on the lint filter in the washing drum and the drain channel and the inside of the drain pipe. The difference in effective chlorine concentration and pH value between the cleaning aqueous solution in the washing drum of Example 19 and the cleaning aqueous solution in the washing machine drum is believed to be due to differences in the amount of water in the program selected by the washing machine, etc.

[0303] The above results show that, compared with the cleaning composition of the comparative example, the cleaning composition of the present invention has extremely high bleaching and cleaning effects on target objects and also has excellent storage stability while suppressing heat generation when a small amount of water is added.

[0304] Comparative Examples 18 to 20

[0305] Sodium dichloroisocyanurate, sodium metasilicate (anhydrous) and sodium metasilicate pentahydrate, as well as tetrasodium ethylenediaminetetraacetic acid dihydrate and trisodium citrate dihydrate, were mixed as other additives according to the formula shown in Table 9 to prepare cleaning compositions having an effective chlorine content ranging from 3.9 to 10%. These cleaning compositions were packaged in aluminum laminated films. The water content, effective chlorine content, pH value of each aqueous solution and heat generation temperature of each cleaning composition are shown in Table 9.

[0306] The water content was calculated using the same method as in the above examples and comparative examples.

[0307]

[0308] As shown in Table 9, the comparison of Comparative Examples 18 to 20 shows that the higher the effective chlorine content of the cleaning composition, the higher the heat generation temperature T 5ml Especially in Comparative Example 20, where the effective chlorine content of the cleaning composition is 10%, the heat generation temperature T 5ml The results show that the higher the effective chlorine content of the cleaning composition, the more intense the heat generation when water is added. Therefore, it can be confirmed that the cleaning composition of the present invention has a significant effect of inhibiting heat generation when used as a cleaning composition with a high effective chlorine content, which is of great significance.

[0309] The present invention can provide a cleaning composition, which can suppress the heat generation when the cleaning composition is dissolved in water, suppress the expansion and rupture of the packaging container containing the cleaning composition, and can stably retain the bleach in the cleaning composition and exert an excellent bleaching effect. The present invention can also provide a cleaning method using the cleaning composition. The cleaning composition of the present invention can achieve the following effects while exerting high-efficiency bleaching and cleaning effects: the effect of suppressing the heat generation when water is added to the cleaning composition; the effect of suppressing the expansion or rupture of the packaging container containing the cleaning composition; and the effect of maintaining a high effective chlorine retention rate in the chlorine bleach. This is a significant effect that the prior art cannot hope to achieve.

[0310] Industrial Applications

[0311] The present invention has industrial applicability because it can provide a cleaning composition which has high bleaching and cleaning effects, suppresses heat generation when water is added to the cleaning composition, suppresses swelling or rupture of a packaging container, and also has excellent storage stability.

Claims

1. A solid cleaning composition comprising: Materials containing coated solid chlorine bleach and alkaline compounds, The cleaning composition has an effective chlorine content of 5% or more, a water content of 40 wt. % or less, and a pH value of a 1 wt. % aqueous solution of the cleaning composition is 9 or more.

2. The cleaning composition according to claim 1, wherein the content of the alkaline compound in the cleaning composition is 5 wt.% or more, provided that when the alkaline compound contains bound water, the bound water is excluded.

3. The cleaning composition according to claim 1 or 2, wherein the sum of the effective chlorine content in the cleaning composition and the content of the alkaline compound is 40 or more, provided that when the alkaline compound contains bound water, the bound water is excluded from the content of the alkaline compound.

4. The cleaning composition according to claim 1 or 2, wherein the ratio of the effective chlorine content to the alkaline compound content in the cleaning composition, i.e., effective chlorine content / alkaline compound content, is in the range of 0.1 to 0.

8.

5. The cleaning composition according to claim 1 or 2, wherein the alkaline compound is at least one selected from the group consisting of metal metasilicates, metal metasilicate hydrates, metal phosphates, metal phosphate hydrates, and mixtures thereof.

6. The cleaning composition according to claim 1 or 2, wherein water from the alkaline compound accounts for 60 wt.% or more of the water content of the cleaning composition.

7. The cleaning composition according to claim 1 or 2, wherein the water content of the cleaning composition is 32 wt.% or less.

8. The cleaning composition according to claim 1 or 2, wherein a pH value of a 1 wt.% aqueous solution of the cleaning composition is 10.5 or higher.

9. A method for cleaning an article, comprising contacting an aqueous solution of the cleaning composition of claim 1 or 2 with the article.

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