JP2007332346A - Granular activated bleaching agent - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a granular activated bleaching agent superior in solubility. <P>SOLUTION: The granular activated bleaching agent contains a bleaching activating agent (a) and a specified alcohol (b) being a liquid at a normal temperature (25°C). <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a granulated product of bleach activator. More specifically, the present invention relates to a granulated product of bleach activator having good solubility and high bleaching performance.

Currently, sodium percarbonate and sodium perborate are mainly used as bleaching bases for bleaching agents and bleaching detergents. However, since sufficient bleaching performance cannot be obtained with these bases alone, bleach activators such as TAED (tetraacetylethylenediamine) and AOBS (sodium alkanoyloxybenzenesulfonate) have come to be used in combination. These bleach activators react with hydrogen peroxide generated from peroxides such as sodium percarbonate to produce organic peracids with strong bleaching power, and are effective in bleaching clothing. The bleach activator is granulated after mixing with a surfactant, a binder, and the like, and may be used by mixing with a detergent for clothing. In such a bleach activator granulated product, for example, Patent Document 1 has been devised to increase the solubility.
Japanese Patent Publication No. 5-440

  However, although this method dissolves relatively quickly under hot water washing conditions, the dissolution rate is slow under cold water conditions, and the function of the bleach activator cannot be fully exploited.

  In addition, in order to increase the dissolution rate of the bleach activator granulated product, a liquid surfactant may be added at room temperature (25 ° C.). In some cases, physical properties such as the caking property of the granulated product deteriorate.

  As described above, diligent research has been conducted to exhibit higher bleaching performance, but it is not yet sufficient, and a bleaching activator granule having improved solubility has been desired. In that case, it is desired that solubility can be improved while satisfying physical properties such as caking properties.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have blended a specific compound that is liquid at room temperature (25 ° C.) with the bleach activator granulated product, thereby producing a bleach activator granulated product. As a result, it was found that the organic peracid production rate was improved and the bleaching performance was improved.

  Furthermore, it has been found that a higher effect can be obtained by coexisting a specific compound that is liquid at normal temperature (25 ° C.) with a nonionic surfactant. As a result, the total compounding amount of the specific compound that is liquid at normal temperature (25 ° C.) and the nonionic surfactant can be suppressed to a smaller amount while improving the solubility. It has been found that the solubility can be improved while satisfying the physical properties.

The present invention is a liquid at room temperature (25 ° C.) selected from the group consisting of (a) component: bleach activator, and (b) component: polyhydric alcohol and a compound represented by the following general formula (I). The present invention relates to a bleach activator granule comprising one or more compounds, and further to a bleach composition containing the bleach activator granule and an inorganic peroxide.
R—O — [(EO) _a / (PO) _b ] —H (I)
(In the formula, R represents a hydrocarbon group having 1 to 8 carbon atoms. EO represents an ethyleneoxy group, PO represents a propyleneoxy group. A and b are average added mole numbers, and each independently represents 0 to 10). (However, a and b are not 0 at the same time.)

  In addition, the present invention is a liquid at room temperature (25 ° C.) selected from the group consisting of (a) component: bleach activator, (b) component: polyhydric alcohol and the compound represented by the above general formula (I). And (c) component: a nonionic surfactant and / or (d) component: a method for producing a bleaching activator granule containing a binder substance, the component (b) It is related with the manufacturing method of the bleaching activator granulation which has the process of mixing the liquid substance containing (a) component.

  According to this invention, the bleaching activator granulated material excellent in solubility is obtained. Furthermore, when using a nonionic surfactant together, solubility can be improved, satisfying physical properties, such as caking. By blending such a bleach activator granulated product of the present invention, the bleaching performance of the bleaching composition or bleaching detergent composition can be improved.

Hereinafter, the components used in the bleaching activator granulated product of the present invention will be described.
<(A) component>
The bleaching activator granulated product of the present invention contains a bleaching activator as the component (a). In the present specification, the bleach activator means a compound that generates an organic peracid by reacting with an inorganic peroxide. Examples of the bleach activator include a compound having an ester bond represented by the following general formula (1).
R ^1a -C (= O) -LG (1)
[Wherein, R ^1a is a hydrocarbon group having 8 to 14 carbon atoms, preferably a linear or branched alkyl group, alkenyl group, aryl group or alkyl group-substituted aryl group, more preferably 10 to 10 carbon atoms. 14 linear or branched alkyl groups. LG is a leaving group. ]
As the leaving group LG, for example,

—O—R ^2a — (O) _p —SO ₃ ^— and —O—R ^2a — (O) _p —SO ₃ M (where R ^2a is an alkylene group, p is 0 or 1, M is a hydrogen atom or an alkali) Represents a metal). The alkylene group for R ^2a preferably has 1 to 5 carbon atoms.

  The bleaching activator in the present invention is not limited to the compound represented by the general formula (1), and any conventionally used bleaching activator can be used. For example, tetraacetylethylenediamine, glucose pentaacetate, tetraacetylglycoluril, alkanoyl or alkenoyl (the number of carbons in these groups is 8 to 14) oxybenzenecarboxylic acid or a salt thereof, alkanoyl or alkenoyl (the number of carbons in these groups is from 8 to 8) 14) oxybenzene sulfonate, and alkanoyl or alkenoyl (the number of these groups is 8 to 14, preferably 10 to 14 from the viewpoint of bleaching effect) oxybenzene carboxylic acid or its salt and alkanoyl or alkenoyl (these The number of carbons in the group is 8 to 14, preferably 10 to 14 from the viewpoint of the bleaching effect, and one or more selected from oxybenzene sulfonates are preferred. These bleach activators can use arbitrary 1 type, or 2 or more types of combination. In particular, decanoyloxybenzenecarboxylic acid or a sodium salt thereof, and dodecanoyloxybenzenesulfonic acid sodium salt are preferred.

  Moreover, it is preferable to use these in powder form, and the bulk density in that case is preferably 0.3 to 0.7 g / ml, more preferably 0.35 to 0.6 g / ml. The average particle size is preferably 0.5 to 200 μm, more preferably 2 to 100 μm, from the viewpoint of granulation and solubility.

  The particle diameter can be measured in acetone using a laser diffraction / scattering particle size distribution meter (manufactured by Nikkiso Co., Ltd., Microtrac HRA). The content of the component (a) in the bleaching activator granule is preferably 10 to 95% by mass from the viewpoint of bleaching performance, and more preferably 50 to 90% by mass from the viewpoint of solubility.

<(B) component>
The bleaching activator granulated product of the present invention is a liquid compound at room temperature (25 ° C.) selected from the group consisting of polyhydric alcohols and compounds represented by the above general formula (I) as component (b). Contains one or more. For example, the component (b) includes a compound selected from linear or branched polyhydric alcohols having 2 to 12, preferably 2 to 9, more preferably 2 to 6 carbon atoms.

  Although it is a polyhydric alcohol in this invention and is not specifically limited as a compound which is liquid at normal temperature (25 degreeC), From a viewpoint of solubility and granulated physical property, glycerin, ethylene glycol, propylene glycol, 1,2,6- Examples include hexanetriol, glycerin, ethylene glycol and propylene glycol are preferred, and glycerin is particularly preferred. These polyhydric alcohols can be used alone or in combination of two or more. Further, from the viewpoint of production, it may be diluted with water or the like.

  Further, the compound represented by the general formula (I) is also a kind of alcohol, and the compound is not particularly limited. However, from the viewpoint of solubility and granulated physical properties, the carbon of R in the general formula (I) The number is more preferably 2 to 5, a is preferably 0 to 5, more preferably 0 to 3, and b is preferably 0 to 5, and particularly preferably 0 to 3. In the general formula (I), EO alone or PO alone may be blended, and EO and PO may be arranged in any form of a random copolymer or a block copolymer.

  Preferred components (b) from the viewpoints of solubility and granulated physical properties include glycerin, ethylene glycol, propylene glycol, 1,2,6-hexanetriol, diethylene glycol monobutyl ether, butylpropylene diglycol, and the like. Ethylene glycol and propylene glycol are preferred, and glycerin is particularly preferred. As these polyhydric alcohol and the compound of general formula (I), arbitrary 1 type (s) or 2 or more types can be used in combination. Further, from the viewpoint of production, it may be diluted with water or the like.

  The component (b) used in the present invention is a compound that is liquid at room temperature (25 ° C.). For example, even if only a polyhydric alcohol such as sorbitol that is solid at 25 ° C. is selected, the effect of improving solubility cannot be found as in Comparative Example 4 described later. The reason why such a difference arises is not necessarily clear, but by adding a substance (component (b)) that is liquid at room temperature to the granulated product as in the present invention, it has an affinity for water during use. Is estimated to improve the dissolution rate.

  The content of the component (b) in the bleaching activator granulated product is preferably 0.1 to 10% by mass from the viewpoint of solubility and granulated physical properties, more preferably 0.1 to 5% by mass, and 0 More preferable is 2 to 2% by mass.

<(C) component>
The bleaching activator granulated product of the present invention may contain a nonionic surfactant as the component (c) from the viewpoints of solubility and granulated physical properties. Examples of the nonionic surfactant of the present invention include a nonionic surfactant obtained by adding an alkylene oxide to an alcohol, particularly a nonionic surfactant represented by the following general formula (3).
^R3a- O [(EO) _c / (PO) _d ] -H (3)
[Wherein, R ^3a represents a hydrocarbon group having 10 to 18 carbon atoms, preferably 12 to 14 carbon atoms, preferably an alkyl group or an alkenyl group. EO represents an ethyleneoxy group, and PO represents a propyleneoxy group. c is an average number of added moles and is a number from 0 to 20, d is an average number of added moles and represents a number from 0 to 20, except when both c and d are 0 at the same time. ]

  In general formula (3), c is preferably 6 to 15, more preferably 7 to 12, and d is preferably 0 to 10, more preferably 1 to 5, and particularly preferably 1 to 3.

  In the general formula (3), EO alone or PO alone may be blended, and EO and PO may be arranged in any form of a random copolymer or a block copolymer.

  The melting point of the component (c) of the present invention is preferably 30 ° C. or less, more preferably 25 ° C. or less, and particularly preferably 20 ° C. or less from the adequacy of mixing during production of the bleach activator granulated product.

  The melting point can be measured by a visual method described in JIS K0064-1992 (pages 1 to 2).

  The nonionic surfactant in the present invention is not particularly limited, but specific examples include Emulgen 507 [EO 7 mol adduct of C12 / C13 mixed alcohol (melting point: 17.5 ° C.)] manufactured by Kao Corporation, Kao Corporation. Emulgen 109P [EO 9.2 mol adduct of C12 alcohol (melting point 21 ° C.)], Emulgen KS-108 [EO 5 mol PO 2 mol EO 3 mol adduct of C12 alcohol (melting point −9 ° C.)], Emulgen KS-110 manufactured by Kao Co., Ltd. [EO7 mol PO2 mol EO3 mol adduct of C12 / C14 mixed alcohol (melting point: 20 ° C.)], Emulgen LS-106 manufactured by Kao Co., Ltd. [EO2.5 mol PO1 of C12 alcohol] 5 mol EO 3 mol adduct (melting point −9 ° C.)] and the like. Among these, an EO / PO addition type nonionic surfactant is preferable from the viewpoint of solubility. Here, EO is ethylene oxide, PO is propylene oxide, and the number of moles added is the average number of moles added.

  The content of the component (c) in the bleaching activator granule is preferably from 0.1 to 10% by mass from the viewpoint of solubility and granulated physical properties, more preferably from 1 to 5% by mass, and from 1 to 3%. More preferred is mass%.

  When the component (c) is used, the total content of the component (b) and the component (c) in the bleach activator granulated product is preferably 1 to 10% by mass from the viewpoint of solubility and granulated physical properties. 2-7 mass% is still more preferable, and 2-5 mass% is still more preferable.

  Moreover, as for mass ratio of (b) component and (c) component, 1.0-0.02 of (b) component is preferable with respect to (c) component 1 from a viewpoint of granulated physical property, 0.7- 0.05 is more preferable.

<(D) component>
The bleaching activator granulated product of the present invention may contain a binder substance as the component (d). The binder substance is not particularly limited as long as it has the ability to bind the components constituting the bleach activator granulated product, but from the viewpoint of solubility of the bleach activator granulated product, water and / or Water-soluble organic substances are preferred. The melting point of the water-soluble organic material is 80 ° C. or less, preferably 70 ° C. or less, more preferably 65 ° C. or less, from the viewpoint of mixing suitability during the production of the bleach activator granulated product. Examples of the water-soluble organic substance include polyalkylene glycol (polyethylene glycol, polypropylene glycol, etc.), saturated or unsaturated fatty acid having 8 to 18 carbon atoms, and the like. You may use these individually or in mixture of 2 or more types. Among these, polyethylene glycol and polypropylene glycol are preferable, and polyethylene glycol is particularly preferable. The average molecular weight of polyethylene glycol and polypropylene glycol is preferably 600 to 20000, more preferably 1000 to 10000, and more preferably 2000 to 6000 from the viewpoint of improving the granulation property of the bleach activator granulated product and the mixing suitability at the time of production. Further preferred. This average molecular weight is a weight average molecular weight measured by gel permeation chromatography (eluent: 0.2 M phosphate buffer containing 10% by mass of acrylonitrile, standard substance: polyethylene glycol).

  Specific examples of the polyalkylene glycol of the present invention include polypropylene glycol (average molecular weight 2000) (melting point 45 to 50 ° C.), polyethylene glycol (average molecular weight 4000) (melting point 50 to 58 ° C.), polyethylene glycol (average molecular weight 6000) ( The melting point is 55 to 62 ° C.), but is not limited thereto.

  From the viewpoint of storage stability, it is particularly preferable to select a water-soluble organic substance so that the bleaching activator granule is solidified at 40 ° C. or lower and has binding properties.

  The melting point can be measured by a visual method described in JIS K0064-1992 (pages 1 to 2).

  The binder substance is preferably 1 to 30% by mass, more preferably 5 to 25% by mass, and particularly preferably 7 to 20% in the granulated product from the viewpoint of improving the granulating property of the bleach activator granulated product. Contains by mass%.

  Further, the binder material is preferably used in an amount of 0.05 to 4 times (mass ratio) with respect to the powder content in the bleach activator granulated product, particularly preferably 0.07 to 3 times. Amount.

<Other ingredients>
The granulation product of the bleach activator of the present invention comprises (a) component, (b) component, further (c) component, (d) component, and other optional components as necessary, for example, bleach base In addition, an inorganic salt such as an enzyme or sodium carbonate, a surfactant other than the component (c), a fluorescent agent, or the like can also be blended. An example is shown below.

(1) Surfactant other than component (c) The bleach activator granulated product of the present invention includes an anionic surfactant, a positive surfactant as a surfactant other than the nonionic surfactant (component (c)). An ionic surfactant and an amphoteric surfactant can be contained. The bleaching activator granulated product of the present invention contains 0 to 50% by mass, more preferably 1 to 20% by mass of one or more selected from anionic surfactants, particularly alkyl sulfates and alkyl ether sulfates. It is desirable. The alkyl sulfate is preferably a sodium salt having 10 to 18 carbon atoms, particularly sodium lauryl sulfate or sodium myristyl sulfate. The alkyl ether sulfate is preferably a polyoxyethylene alkyl ether sulfate having 10 to 18 carbon atoms in the alkyl group, and a sodium salt is preferable. Here, the degree of polymerization (POE) of the polyoxyethylene group is 1 to 10 on average, preferably 1 to 5 on average. Particularly, polyoxyethylene (POE = average 2 to 5) sodium lauryl ether sulfate, polyoxyethylene ( POE = average 2-6) sodium myristyl ether sulfate is good.

(2) Solid or powdered acid (stabilizer)
In the bleaching activator granulated product of the present invention, a solid or powdered acid may be added as a stabilizer for the bleach activator. The type is not particularly limited, and for example, formic acid, succinic acid, fumaric acid, citric acid, phosphoric acid, zeolite showing solid acidity, and the like can be mentioned, among which succinic acid and citric acid are preferable. These acids may form a salt, and the counter ion is an alkali metal ion, an ammonium ion, or the like. These contents are preferably 0.5 to 10% by mass and more preferably 1 to 5% by mass in the bleaching activator granulated product of the present invention.

(3) Recontamination inhibitor The bleach activator granulated product of the present invention can be granulated by blending a recontamination inhibitor. In this case, the recontamination preventive agent is not particularly limited, but a recontamination preventive agent such as polyvinyl alcohol, polyvinyl pyrrolidone, carboxymethyl cellulose and the like can be added as necessary.

(4) Dissolution Accelerator The bleach activator granulated product of the present invention can be granulated with a dissolution accelerator added. In this case, the dissolution accelerator is not particularly limited, but a dissolution accelerator such as urea, urea derivative, thiouric acid, paratoluenesulfonate, water-soluble inorganic salts, and the like can be added as necessary.

(5) Excipients The granulation product of the bleaching activator of the present invention can be added with an inorganic salt such as bousho or zeolite as an excipient for the purpose of improving granulation properties and the like. In this case, the amount used is preferably 1 to 40% by mass, and more preferably 5 to 20% by mass. The average particle size is preferably about 1 to 100 μm.

(6) Colorant The bleaching activator granulated product of the present invention may be blended with a pigment, a dye, or the like as a colorant for the purpose of improving the appearance or the like. As such a colorant, for example, phthalocyanine green (CIPigment 7, 36, 37, 38, etc.) or ultramarine blue (CIPigment Bule 29, etc.) can be used, and the blending amount is 0.01 to 1 mass in the granulated product. %, Particularly 0.05 to 0.5% by mass is preferred.

(7) Surface coating agent The bleaching activator granulated product of the present invention may be subjected to surface modification with a surface coating agent from the viewpoint of fluidity and non-caking property. Examples of the surface coating agent include aluminosilicate, calcium silicate, silicon dioxide, bentonite, talc, clay, amorphous silica derivative, crystalline silicate compound such as silicate compound, metal soap, powdered surfactant, etc. Body, carboxymethylcellulose, sodium polyacrylate, water-soluble polymers such as polycarboxylic acid salts such as copolymers of acrylic acid and maleic acid or salts thereof, fatty acids, and the like.

The granulation method of the bleaching activator granulated product of the present invention will be described.
The bleaching activator granulated product of the present invention can be produced by mixing the component (a) and the component (b). Furthermore, the bleaching activator granulated product of the present invention can be produced by mixing the component (a), the component (b), the component (c), and the component (d). For example, the component (a), the component (b), the component (c), and the component (d) can be melt-mixed, and then the resulting mixture is granulated such as extrusion granulation.

  The granulated product of the bleach activator of the present invention is preferably produced by a production method having a step of mixing a liquid material containing the component (b) with the component (a). The liquid containing the component (b) preferably contains the component (b), the component (c) and / or the component (d). The liquid material may contain components that are in a molten state by heating, and may contain components other than the components (b), (c), and (d).

In particular,
(I): a method of simultaneously adding and mixing the component (a) and the component (d) to the liquid mixture of the component (b) and the component (c),
(Ii): A liquid mixture of (b) component and (c) component is added to either (a) component or (d) component, and then the other of (a) component or (d) component is added how to,
(Iii): A method of adding a liquid mixture of the component (b) and the component (c) to the mixture of the component (a) and the component (d). Among these, in particular, from the viewpoint of mixing suitability at the time of production, the above method (ii), particularly the liquid mixture of the component (a) and the component (b) and the component (c) is first mixed, Furthermore, the method of adding (d) component is preferable.

As another specific example,
(1): a method of simultaneously adding and mixing the component (a) and the component (c) to the liquid mixture of the component (b) and the component (d),
(2): Add a liquid mixture of the component (b) and the component (d) to either the component (a) or the component (c), and then add the other of the component (a) or the component (c) how to,
(3): A method of adding a liquid mixture of the component (b) and the component (d) to the mixture of the component (a) and the component (c). Among these, in particular, from the viewpoint of mixing suitability during production, a liquid mixture of the component (b) and the component (d) is added to the mixture of the component (a) and the component (c) as in the above (3). The method is preferred.

  The granulation method is not particularly limited, and a general granulation method can be used using a conventionally known granulation apparatus. For example, it can be produced by a stirring rolling granulation method, an extrusion granulation method, a spray cooling method or the like. Examples of the apparatus used for granulation include a high-speed mixer manufactured by Fukae Kogyo Co., Ltd. and a pro-shear mixer manufactured by Taiheiyo Kiko Co., Ltd. Examples include Pelleter Double and Twin Dome Gran manufactured by Nipowdaru.

  The temperature during granulation is in the vicinity of the melting point of component (c) or component (d) in order to suppress the generation of fine powder and to give an appropriate particle strength, and more specifically, component (c) or component (d) It is preferable to extrude in a temperature range from 20 ° C. to 5 ° C. lower than the melting point of the components. At that time, for example, the screen is selected so that the average particle diameter is 700 μm to 1500 μm, and the extrusion pressure is adjusted so that the bulk density is 0.5 to 0.8 g / mL.

  As another granulation method, a tablet shape by a briquetting machine can be cited as a preferable granulation method.

  In the present invention, after granulation, if necessary, granulation may be performed by crushing, spheroidizing, or the like. Examples of the device used for crushing include a flash mill manufactured by Fuji Paudal Co., Ltd., a Fitz mill manufactured by Fitzpatrick (USA), etc., and a device used for spheroidizing such as a Malmerizer manufactured by Fuji Powdal Co., Ltd. Is mentioned. The temperature supplied to the pulverizer is preferably cooled to near room temperature. For example, when the granulated material is supplied to the vibration cooler and pulverized after cooling to a predetermined temperature, the crushed material adheres within the pulverizer. Is suppressed. Further, in order to further reduce fine powder generated by crushing and spheronization and coarse powder that has not been sufficiently crushed and spheroidized, the crushed material may be further classified.

  Although the particle diameter of the bleaching activator granulated product in the present invention is not particularly limited, the average particle diameter is preferably 100 to 5000 μm, more preferably 200 to 2000 μm from the viewpoint of appearance and solubility. The particle shape is most preferably spherical from the viewpoints of appearance and classification, and in the case of an extruded granulated product that is not spheroidized, the ratio of the extruded diameter to the length is preferably close to 1.

<Bleach composition>
The bleaching agent composition of the present invention contains the above-mentioned bleaching activator granulated product (I) and inorganic peroxide (II), and when used as a bleaching detergent composition, it further comprises a surfactant. Contains contained detergent particles (III).

[Inorganic peroxide (II)]
Examples of the inorganic peroxide (II) used in the present invention include perborates and percarbonates, and percarbonate is particularly preferred from the viewpoint of environmental safety. When a percarbonate is used in a composition containing zeolite, for example, a percarbonate coated with at least one selected from paraffin, borate, perborate, ethylene oxide adduct of alcohol, polyethylene glycol, and silicate compound is used. preferable.

[Surfactant-containing detergent particles (III)]
In the present invention, surfactant-containing detergent particles (III) can be blended in the bleaching composition for the purpose of imparting cleaning performance. Examples of the surfactant include an anionic surfactant, a nonionic surfactant, an amphoteric surfactant, and a cationic surfactant. Specifically, alkylbenzene sulfonate, alkyl sulfate, alkyl ether sulfate, olefin sulfonate, alkane sulfonate, fatty acid salt, alkyl or alkenyl ether carboxylate, α-sulfo fatty acid salt or ester thereof, etc. Anionic surfactant, polyoxyethylene or polyoxypropylene or copolymers thereof, polyoxyethylene alkyl or alkenyl ether, polyoxyethylene alkyl phenyl ether, higher fatty acid alkanolamide or its alkylene oxide adduct, sucrose fatty acid ester, alkyl glucoside And nonionic surfactants such as amine oxide, sulfobetaine and carbobetaine, and cationic surfactants such as quaternary ammonium salts. The surfactant is preferably blended in the surfactant-containing detergent particles by 10 to 60% by mass, particularly preferably 20 to 50% by mass.

  In the bleaching agent composition of the present invention, the bleaching activator granulated product (I) is preferably 1 to 30% by mass, more preferably 3 to 20% by mass, and the inorganic peroxide (II) is preferably 20 to 95%. It is contained by mass%, more preferably 30 to 90 mass%. Moreover, the bleaching detergent composition in the case of mix | blending surfactant-containing detergent particle | grains (III) becomes like this. Preferably bleach activator granulation (I) is 0.1-10 mass%, More preferably, it is 0.3. -8% by mass, preferably 0.5 to 30% by mass of inorganic peroxide (II), more preferably 1 to 20% by mass, and preferably 60 to 99.4% by mass of surfactant-containing detergent particles (III). %, More preferably 70 to 97% by mass.

  Further, in the present invention, the mass ratio of the bleach activator granulated product (I) and the inorganic peroxide (II) is (I) / (II) = 2/1 to 1/20, particularly from the viewpoint of the bleaching effect. 1/1 to 1/15 is preferable.

  In this invention, 1-50 mass%, Preferably 5-40 mass% can be mix | blended with sodium carbonate in a bleach composition or a bleaching detergent composition. For example, light ash, dense ash and the like can be mentioned. Among them, dense ash having an average particle size of 300 ± 200 μm, particularly 300 ± 100 μm is preferable.

  In the present invention, crystalline aluminosilicates such as A-type, X-type, and P-type zeolite are added in an amount of 40% by mass or less, more preferably 1%, in the bleaching composition or bleaching detergent composition in order to enhance the bleaching washing effect. -40 mass% can be mix | blended. In particular, A-type zeolite is preferable. The average primary particle diameter is preferably 0.1 to 10 μm, particularly 0.1 to 5 μm.

  In the present invention, a metal sequestering agent is blended in the bleaching composition or the bleaching detergent composition in an amount of 0.0005 to 30% by mass, more preferably 0.01 to 15% by mass for the purpose of measuring the stability of the inorganic peroxide. can do. As the metal sequestering agent, (1) a phosphoric acid compound such as phytic acid or a salt thereof, (2) ethane-1,1-diphosphonic acid, ethane-1,1,2-triphosphonic acid, ethane-1-hydroxy-1 , 1-diphosphonic acid and derivatives thereof, phosphonic acids such as ethanehydroxy-1,1,2-triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid, methanehydroxyphosphonic acid or salts thereof ( 3) Phosphonocarboxylic acid such as 2-phosphonobutane-1,2-dicarboxylic acid, 1-phosphonobutane-2,3,4-tricarboxylic acid, α-methylphosphonosuccinic acid or salts thereof, (4) aspartic acid, glutamic acid , Amino acids such as glycine or salts thereof, (5) nitrilotriacetic acid, iminodiacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, glycolate Aminopolyacetic acid or its salts such as terdiaminetetraacetic acid, hydroxyethyliminodiacetic acid, triethylenetetraaminehexaacetic acid, diencoric acid, (6) organic acids such as diglycolic acid, oxydisuccinic acid, carboxymethyloxysuccinic acid, carboxymethyltartaric acid Or salts thereof, (7) aminopoly (methylenephosphonic acid) or polyethylenepolyaminepoly (methylenephosphonic acid), or salts thereof.

  Among these, one or more selected from the group consisting of the above (2), (5) and (6) is preferable, and the above (2) and (5) are particularly preferable.

  In the present invention, enzymes such as protease, cellulase, pectinase, amylase, and lipase can be blended in the bleaching composition or the bleaching detergent composition for the purpose of improving the bleaching effect. In particular, it is preferable to use one or more proteases or cellulases. Examples of cellulases include bacterial cellulases and fungal cellulases, and those having an optimum pH of 5 to 9.5 are particularly preferable. For example, those described in JP-A 63-264699, page 4, upper right column, line 13 to page 5, lower right column, line 12 can be used, and particularly alkaliphilic microorganisms Bacillus sp. KSM-635 (FERM BP- 1485) or an alkaline cellulase produced from a mutant strain thereof is preferably used. Moreover, the cellulase of the 5th column 3rd line-21st line of Unexamined-Japanese-Patent No. 8-53699 can also be used. More specifically, enzyme granulated products such as KAC500 (registered trademark) manufactured by Kao Corporation and Cellzyme (registered trademark) manufactured by Novo Nordisk can be mentioned. The protease is preferably an alkaline protease having an optimum pH of 8 or more, preferably 8-11. Examples include Alcalase, Sabinase (Novo Nordisk, registered trademark), Perfect (Genenco, registered trademark), KAP4.3G, KAP11.1G (all registered trademark, Kao Corporation), and the like. However, KAP4.3G and KAP11.1G are particularly excellent. The enzyme is blended in the bleaching composition or the bleaching detergent composition in an amount of 0.005 to 3% by mass, preferably 0.01 to 2% by mass as the enzyme bulk powder in terms of the cleaning effect. When protease and cellulase are used in combination, the mass ratio of protease to cellulase is preferably 1/50 to 1/1, preferably 1/30 to 1/2, based on the enzyme bulk powder.

  These optional components are included in the bleaching agent composition or bleaching detergent composition, and the bleach activator granulated product (I), inorganic peroxide (II) and / or surfactant-containing detergent as described above. The particles (III) may be blended separately as an after blend, or may be blended in the bleach activator granule (I) and / or the surfactant-containing detergent particles (III). The surfactant-containing detergent particles (III) may contain a bleach activator. However, it is preferable that the bleach activator is less than 40% by mass, more preferably 10% by mass or less, and particularly substantially not contained in the particles.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, it is not limited to these Examples. Unless otherwise specified,% in the examples is based on mass.

Example 1
Bleach activator of the following formula (I) [hereinafter referred to as bleach activator (I)] 8.45 kg, succinic acid (manufactured by Kawasaki Kasei Kogyo Co., Ltd.) 0.26 kg, glycerin (manufactured by Kao Corporation: Japan Pharmacopoeia) ) Charge 0.39kg into a blender (Hosokawa Micron Co., Ltd .: Nauter Mixer NX-S), mix and heat at a jacket temperature of 80 ° C, rotation speed of 121rpm, revolution speed of 5.5rpm, and the temperature of the powder When the temperature reached 60 ° C., 3.9 kg of polyethylene glycol (manufactured by Kao Corporation: K-PEG6000LA) previously melted at 70 ° C. was added, and further mixed for 25 minutes, and then the mixture was extracted. Next, the obtained mixture was extruded through a screen having a pore diameter of 700 μm by an extrusion granulator (Fuji Powdal: Pelletter Double EXD-60) to be consolidated. After cooling the extrudate obtained, it is crushed with a granulator (Fujipowder: Flash Mill FL200), and the particle size is adjusted to 350-1410 μm by classification to obtain a bleach activator granulated product. It was.

Example 2
Bleach activator (I) 8.45 kg, anionic surfactant (manufactured by Kao Corporation: Emar 10 powder (hereinafter referred to as E-10P)) 1.5 kg, succinic acid (manufactured by Kawasaki Chemical Industry Co., Ltd.) 0.26 kg, glycerin (Kao Co., Ltd .: Japan Pharmacopoeia) 0.59kg was charged into a blender (Hosokawa Micron Co., Ltd .: Nauter Mixer NX-S type), jacket temperature 80 ° C, rotation speed 121rpm, revolution speed Mix and heat up at 5.5 rpm, and when the temperature of the powder reaches 60 ° C, add 2.21 kg of polyethylene glycol (K-PEG6000LA) previously melted at 70 ° C and mix for another 25 minutes. After doing so, the mixture was extracted. Next, the obtained mixture was extruded through a screen having a pore diameter of 700 μm by an extrusion granulator (Fuji Powdal: Pelletter Double EXD-60) to be consolidated. After cooling the extrudate obtained, it is crushed with a granulator (Fujipowder: Flash Mill FL200), and the particle size is adjusted to 350-1410 μm by classification to obtain a bleach activator granulated product. It was.

Example 3
Nonionic surfactant (Kao Co., Ltd .: Emulgen KS108S95) 0.65 kg and glycerin (Kao Co., Ltd .: Japan Pharmacopoeia) 0.39 kg premix, bleach activator (I) 8.45 kg, succinic acid ( (Kawasaki Kasei Kogyo Co., Ltd.) 0.26kg was charged into a blender (Hosokawa Micron Co., Ltd .: Nauter Mixer NX-S), mixed at a jacket temperature of 80 ° C, rotating at 121rpm, and revolving at 5.5rpm. When the temperature of the powder reaches 60 ° C, add 3.25 kg of polyethylene glycol (K-PEG6000LA), previously melted at 70 ° C, and mix for another 25 minutes, then extract the mixture. It was. Next, the obtained mixture was extruded through a screen having a pore diameter of 700 μm by an extrusion granulator (Fuji Powdal: Pelletter Double EXD-60) to be consolidated. After cooling the extrudate obtained, it is crushed with a granulator (Fujipowder: Flash Mill FL200), and the particle size is adjusted to 350-1410 μm by classification to obtain a bleach activator granulated product. It was.

Example 4
Non-ionic surfactant (Kao Co., Ltd .: Emulgen KS108S95) 0.33 kg and glycerin (Kao Co., Ltd .: Japan Pharmacopoeia) 0.13 kg premix, bleach activator (I) 9.49 kg, anionic interface Activator (Kao Co., Ltd .: E-10P) 1.50 kg, succinic acid (Kawasaki Chemical Industry Co., Ltd.) 0.26 kg was charged into a blender (Hosokawa Micron Co., Ltd .: Nauter Mixer NX-S type) Polyethylene glycol (Made by Kao Corporation: K), which was mixed and heated at a jacket temperature of 80 ° C, a rotation speed of 121 rpm, and a revolution speed of 5.5 rpm, and was previously melted at 70 ° C when the powder temperature reached 60 ° C. -PEG6000LA) 1.3 kg was added, and after further mixing for 25 minutes, the mixture was extracted. Next, the obtained mixture was extruded through a screen having a pore diameter of 700 μm by an extrusion granulator (Fuji Powdal: Pelletter Double EXD-60) to be consolidated. After cooling the extrudate obtained, it is crushed with a granulator (Fujipowder: Flash Mill FL200), and the particle size is adjusted to 350-1410 μm by classification to obtain a bleach activator granulated product. It was.

Example 5
The amount of glycerin (manufactured by Kao Corporation: Japanese Pharmacopoeia) was changed to 0.26 kg, the amount of nonionic surfactant (manufactured by Kao Corporation: Emulgen KS108S95) was changed to 0.26 kg, and polyethylene glycol (Kao ( A granulated product was prepared under the same conditions as in Example 4 except that the amount of K-PEG6000LA) was changed to 1.24 kg.

Example 6
The amount of glycerin (manufactured by Kao Corporation: Japanese Pharmacopoeia) was changed to 0.026 kg, the amount of nonionic surfactant (manufactured by Kao Corporation: Emulgen KS108S95) was changed to 0.65 kg, and polyethylene glycol (Kao ( A granulated product was produced under the same conditions as in Example 4 except that the amount of K-PEG6000LA) was changed to 1.08 kg.

Example 7
The amount of bleach activator (I) was changed to 9.1 kg, the amount of glycerin (manufactured by Kao Corporation: Japanese Pharmacopoeia) was changed to 0.26 kg, and an anionic surfactant (manufactured by Kao Corporation: E) -10P) was changed to 1.69kg, the amount of succinic acid (Kawasaki Chemical Industries Co., Ltd.) was changed to 0.39kg, and the amount of polyethylene glycol (Kao Co., Ltd .: K-PEG6000LA) was changed to 1.17kg. The nonionic surfactant was changed from Emulgen KS108S95 manufactured by Kao Co., Ltd. to Emulgen KS110S95 manufactured by Kao Co., Ltd., and 0.39 kg of this nonionic surfactant (Eugengen KS110S95 manufactured by Kao Co., Ltd.) was added. A granulated material was produced under the same conditions as in Example 4.

Example 8
A granulated product was produced under the same conditions as in Example 7 except that 0.26 kg of diethylene glycol monobutyl ether was blended in place of glycerin.

Example 9
A granulated product was produced under the same conditions as in Example 7 except that 0.26 kg of ethylene glycol was blended in place of glycerin.

Example 10
A granulated product was produced under the same conditions as in Example 7 except that 0.26 kg of propylene glycol was blended in place of glycerin.

Example 11
The amount of bleach activator (I) was changed to 9.75 kg, the amount of glycerin (Kao Corporation: Japan Pharmacopoeia) was changed to 0.065 kg, and the nonionic surfactant (Kao Corporation: Emulgen) The amount of KS108S95) was changed to 0.46 kg, the amount of anionic surfactant (Kao Corporation: E-10P) was changed to 1.43 kg, and polyethylene glycol (Kao Corporation: K-PEG6000LA) A granulated material was produced under the same conditions as in Example 4 except that the amount was changed to 1.04 kg.

Example 12
A granulated product was produced under the same conditions as in Example 7 except that 9.1 kg of tetraacetylethylenediamine was blended in place of the bleach activator (I).

Comparative Example 1
Bleaching activator (I) 8.45kg and succinic acid (Kawasaki Chemical Industry Co., Ltd.) 0.26kg were charged into a blender (Hosokawa Micron Co., Ltd .: Nauter Mixer NX-S type), jacket temperature 80 ° C, rotation Mixing and heating at 121 rpm, revolution speed 5.5 rpm, 4.29 kg of polyethylene glycol (K-PEG6000LA manufactured by Kao Co., Ltd.) previously melted at 70 ° C. when the temperature of the powder reached 60 ° C. In addition, after further mixing for 25 minutes, the mixture was extracted. Next, the obtained mixture was extruded through a screen having a pore diameter of 700 μm by an extrusion granulator (Fuji Powdal: Pelletter Double EXD-60) to be consolidated. After cooling the extrudate obtained, it is crushed with a granulator (Fujipowder: Flash Mill FL200), and the particle size is adjusted to 350-1410 μm by classification to obtain a bleach activator granulated product. It was.

Comparative Example 2
Bleaching activator (I) 9.49 kg, anionic surfactant (Kao Co., Ltd .: E-10P) 1.24 kg, succinic acid (Kawasaki Chemical Industry Co., Ltd.) 0.26 kg blender (Hosokawa Micron Co., Ltd.) Manufactured: Nauta mixer NX-S type), mixed and heated at a jacket temperature of 80 ° C, a rotation speed of 121rpm, and a revolution speed of 5.5rpm. When the temperature of the powder reaches 60 ° C, it is 70 ° C in advance. After adding 2.02 kg of polyethylene glycol (KoPEG Co., Ltd .: K-PEG6000LA) melted in Step 2, the mixture was further extracted for 25 minutes, and then the mixture was extracted. Next, the obtained mixture was extruded through a screen having a pore diameter of 700 μm by an extrusion granulator (Fuji Powdal: Pelletter Double EXD-60) to be consolidated. After cooling the extrudate obtained, it is crushed with a granulator (Fujipowder: Flash Mill FL200), and the particle size is adjusted to 350-1410 μm by classification to obtain a bleach activator granulated product. It was.

Comparative Example 3
A granulated material was produced under the same conditions as in Example 7 except that the amount of polyethylene glycol (Kao Corporation: K-PEG6000LA) was changed to 1.43 kg and glycerin was not blended.

Comparative Example 4
A granulated product was produced under the same conditions as in Example 7 except that 0.26 kg of sorbitol was used instead of glycerin.

Comparative Example 5
A granulated product was produced under the same conditions as in Example 11 except that the amount of the nonionic surfactant (Kao Co., Ltd .: Emulgen KS108S95) was changed to 0.52 kg and glycerin was not blended.

Comparative Example 6
A granulated material was produced under the same conditions as in Example 12 except that the amount of polyethylene glycol (Kao Corporation: K-PEG6000LA) was changed to 1.43 kg and glycerin was not blended.

  The dissolution time and caking property of the bleaching activator granules obtained in Examples and Comparative Examples are shown in Tables 1-6. Moreover, about some granulated products, the organic peracid production rate was also measured. In addition, these evaluation was performed with the following method.

<Dissolution time>
Using ion-exchanged water having a water temperature of 20 ° C. or 10 ° C., 7% by mass of the bleaching activator granulated product obtained in Examples or Comparative Examples was added and stirred and mixed with a magnetic stirrer (stirrer piece: length 30 mm, The change in electric conductivity of ion-exchanged water was measured over time with an electric conductivity meter. After confirming that the bleaching activator granulated product in ion-exchanged water is not left undissolved, calculate the dissolution rate (%) by the following formula and calculate the time required to dissolve 90% (by mass) T-90 It was shown as dissolution time.
Dissolution rate (%) = (electric conductivity value / maximum value of electric conductivity) × 100

<Caking properties>
In a paper box with a length of 10 cm, a width of 6 cm, and a height of 4 cm, 120 g of the bleaching activator granulated product obtained in the example or the comparative example is placed, dropped with an acrylic plate of 9.5 cm in length and 5.5 cm in width and covered. Then, a 250 g weight was placed on the lid and stored in an environment of 30 ° C./50% Rh for 4 days. Thereafter, the weight and the acrylic plate were removed, and the degree of clumping of the bleaching activator granulated product was determined visually and by hand as follows.
I ... There is almost no mass.
II ... Slightly agglomerate occurs, but with a slight touch, the agglomerate collapses and returns to granular form.
III ... Many lumps occur.
IV: It hardens as a whole and there is a problem with handling.

<Method for measuring organic peracid production rate>
1L of ion-exchanged water is put into a 1L beaker, and 3ml of 5% by weight aqueous solution of LAS (sodium dodecylbenzenesulfonate), 3ml of 5% by weight aqueous solution of sodium carbonate, and 10ml of 0.2% by weight aqueous solution of hydrogen peroxide. The added aqueous solution was stirred (100 rpm) for 1 minute with a magnetic stirrer (using a cylindrical stirrer piece having a diameter of 10 mm and a length of 30 mm). Thereafter, 0.05 g of the bleaching activator granulated product obtained in Examples or Comparative Examples was added and stirred for an arbitrary time (2 minutes, 5 minutes, and 10 minutes), and 10 ml of 0.3% catalase aqueous solution. And stirred for another 1 minute. To this solution, 10 ml of 10% by weight potassium iodide solution and 20 ml of 20% by weight sulfuric acid solution were added. Next, titration was performed with a 0.02 mol / l sodium thiosulfate solution, and the organic peracid production rate was calculated by the following equation. The results are shown in FIGS.

  In the formula, the effective amount of the bleach activator is the mass (g) of the bleach activator in the bleach activator granule. However, when the bleach activator is tetraacetylethylenediamine, it is possible to produce two molecules of organic peracid from one molecule, so the mass (g) of the bleach activator in the bleach activator granulated product 2 times the effective amount of bleaching activator.

Examples 13 to 16 and Comparative Examples 7 to 8
Bleach compositions and bleach detergent compositions were prepared using some of the bleach activator granules obtained in Examples 1 to 12 and Comparative Examples 1 to 6, and the following evaluations were performed. The components used for the preparation of each composition are as follows.

(1) Inorganic peroxide Sodium percarbonate coated with sodium metaborate tetrahydrate according to Example 1 of JP-A-59-196399 (5% coating). Sodium percarbonate used was made by Nippon Peroxide.

(2) Surfactant-containing detergent particles Linear alkyl (12 carbon atoms) benzenesulfonic acid sodium 2000 g, sodium lauryl sulfate 500 g, polyoxyethylene alkyl ether (Nippon Shokubai Emulgen 510L), acrylic acid-maleic acid copolymer (BASF) Sokaran cp-5) 300 g, beef tallow fatty acid sodium 300 g, sodium carbonate 600 g, No. 1 silicate 1500 g, 4A type zeolite 1500 g, balance amount of sodium nitrate, PEG (weight average molecular weight 13000) 100 g to 50% solids water slurry The particles obtained by spray-drying (drying temperature 190 ° C.) were put into a high speed mixer (FS-GC-10 manufactured by Fukae Kogyo Co., Ltd.) and further polyoxyethylene lauryl ether (EO average added mole number 8). ) 500g, 4A type Surfactant-containing detergent particles obtained by adding 1500 g of zeolite and granulating. Average particle size: 430 μm, bulk density: 780 g / L.

(3) Other components / alkaline protease: KAP4.3G manufactured by Kao Corporation
・ Sodium carbonate: manufactured by Central Glass Co., Ltd. ・ Sodium sulfate: manufactured by Shikoku Kasei Co., Ltd.

  The bleaching composition shown in Table 7 below contains a bleach activator granulated product and an inorganic peroxide, and the bleaching detergent composition shown in Table 8 contains a bleach activator granulated product and an inorganic peroxide. And a surfactant-containing detergent particle. Regarding the bleaching composition shown in Table 7 and the bleaching detergent composition shown in Table 8, the organic peracid production rate and the bleaching performance (dipping conditions or washing conditions) were evaluated by the following methods.

<Bleaching performance (1): Soaking conditions>
The bleach composition was dissolved in 500 ml of tap water at 10 ° C. so that the concentration of the bleach activator was 0.05% by mass, and 30 pieces of curry-stained cloth (lipophilic soil) prepared as follows were each 30 Immerse for a minute. Thereafter, it was rinsed with tap water and dried, and the bleaching rate was calculated by the following formula.

  The reflectance was measured using NDR-10DP manufactured by Nippon Denshoku Industries Co., Ltd. using a 460 nm filter.

(Preparation of curry contaminated cloth)
After removing the solid content of the house food retort curry (curry marche) with a mesh, the resulting liquid was heated until boiling. Cotton gold cloth # 2003 was immersed in this solution and boiled for about 15 minutes. After removing from the fire as it was for about 2 hours and leaving it to room temperature, the cloth was taken out, the excess curry liquid was removed with a spatula and allowed to dry naturally. After that, it was pressed and subjected to an experiment as a 10 cm × 10 cm test piece.

<Bleaching performance (2): washing conditions>
Dissolve the bleach detergent composition in 1 L of tap water at 10 ° C. so that the concentration of the bleach activator is 0.003% by mass, and put 5 sheets of curry-stained cloth (lipophilic soil) prepared as described above. Washing was performed at 100 rpm with a targotometer. The washing conditions were washing time: 10 minutes, hardness: 4-DH, water temperature: 10 ° C., rinsing: tap water in 5 minutes. The bleaching rate was calculated by the same method as above.

<Method for measuring organic peracid production rate>
A 1 L beaker is charged with 1 L of ion-exchanged water, and an aqueous solution obtained by adding 3 ml of a 5% by weight aqueous solution of LAS (sodium dodecylbenzenesulfonate) and 3 ml of a 5% by weight aqueous solution of sodium carbonate to a magnetic stirrer (diameter 10 mm, length) The mixture was stirred for 1 minute (100 rpm) using a 30 mm cylindrical stirrer piece. Then, after adding the bleaching agent composition obtained by the Example or the comparative example so that a bleaching activator granulation material may be 0.05 g and stirring for 5 minutes, 10 ml of 0.3% catalase aqueous solution was added. In addition, the mixture was further stirred for 1 minute. To this solution, 10 ml of 10% by weight potassium iodide solution and 20 ml of 20% by weight sulfuric acid solution were added. Next, titration was performed with a 0.02 mol / l sodium thiosulfate solution, and the organic peracid production rate was measured by the following equation.

  In the formula, the effective amount of the bleach activator is the mass (g) of the bleach activator in the bleach activator granule.

  Since the dissolution time varies depending on the content of the bleach activator in the granulated product, it is necessary to compare the bleach activator content in the granulated product with the same content in the above Examples and Comparative Examples.

  From the comparison of the dissolution times of Example 1 and Comparative Example 1 in Table 1, it can be seen that the solubility of the granulated product is increased by blending a specific compound that is liquid at room temperature (25 ° C.) of the component (b). Moreover, it turns out from the comparison with Examples 4-6 of Table 2 and the comparative example 2 that solubility further increases by using together the nonionic surfactant of (c) component.

  From the results of measuring the organic peracid production rate shown in FIGS. 1 and 2, in the bleaching activator granulated product of Example 7 containing the components (b) and (c), the bleaching activator granulation of Comparative Example 3 was used. It can be seen that the organic peracid production rate is higher than the product, and the bleaching performance evaluation results shown in Table 7 show that the bleaching performance is also high. From this, the bleaching activator granulated product of the present invention is improved in solubility by blending the component (b), and as a result, the organic peracid production rate contributing to clothing bleaching is increased, thereby increasing the bleaching performance. Is estimated to improve.

  Further, the bleaching activator granulated product of the present invention is remarkably improved in solubility at a low temperature, and can improve the bleaching performance and reduce the unsettled residue of the bleach activator granulated product.

The graph which shows the relationship between the stirring time in 20 degreeC of the bleaching activator granulated material obtained in Example 7 and Comparative Example 3, and an organic peracid production rate The graph which shows the relationship between the stirring time in 10 degreeC of the bleaching activator granulated material obtained in Example 7 and Comparative Example 3, and an organic peracid production rate

Claims (13)

(A) Component: Bleach activator, and (b) Component: One type of compound that is liquid at room temperature (25 ° C.) selected from the group consisting of polyhydric alcohols and compounds represented by the following general formula (I) A bleach activator granulated product comprising the above.
R—O — [(EO) _a / (PO) _b ] —H (I)
(In the formula, R represents a hydrocarbon group having 1 to 8 carbon atoms. EO represents an ethyleneoxy group, PO represents a propyleneoxy group. A and b are average added mole numbers, and each independently represents 0 to 10). (However, a and b are not 0 at the same time.) The bleaching activator granulated product according to claim 1, wherein the component (b) is a polyhydric alcohol that is liquid at normal temperature (25 ° C). The bleaching activator granulated product according to claim 1 or 2, wherein the component (b) is one or more polyhydric alcohols selected from the group consisting of ethylene glycol, glycerin, and propylene glycol. Furthermore, (c) component: The bleaching activator granulated material of any one of Claims 1-3 containing a nonionic surfactant. Furthermore, (d) component: Bleach activator granulated material of any one of Claims 1-4 containing a binder substance. The bleach activator granulated product according to claim 5, wherein the binder material of component (d) is polyalkylene glycol. The weight average molecular weight of (d) component is 600-20000, The bleaching activator granulated material of Claim 5 or 6. The component (b) contains 0.1 to 10% by mass, (c) the component 0.1 to 10% by mass, and (d) the component 1 to 30% by mass. The bleach activator granulated product described. The bleaching activator granulated product according to any one of claims 5 to 8, wherein the component (c) has a melting point of 30 ° C or lower and the component (d) has a melting point of 80 ° C or lower. A bleaching agent composition comprising the bleaching activator granulated product according to any one of claims 1 to 9 and an inorganic peroxide. The bleach composition according to claim 10, further comprising surfactant-containing detergent particles. Component (a): Bleach activator, Component (b): One or more compounds selected from the group consisting of polyhydric alcohols and compounds represented by the following general formula (I), which are liquid at room temperature (25 ° C.) And (c) component: a nonionic surfactant and / or (d) component: a method for producing a bleaching activator granule containing a binder substance,
(B) The manufacturing method of the bleaching activator granulation which has the process of mixing the liquid containing a component with (a) component.
R—O — [(EO) _a / (PO) _b ] —H (I)
(In the formula, R represents a hydrocarbon group having 1 to 8 carbon atoms. EO represents an ethyleneoxy group, PO represents a propyleneoxy group. A and b are average added mole numbers, and each independently represents 0 to 10). (However, a and b are not 0 at the same time.)   The manufacturing method of the bleaching activator granulated material of Claim 12 in which the liquid substance containing (b) component contains (b) component, (c) component, and / or (d) component.

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