JP2009126932A - Granular bleaching activator - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a granular bleaching activator that exhibits excellent solubility. <P>SOLUTION: The granular bleaching activator comprises (a) a bleaching activator and (b) a compound represented by general formula (1): R<SP>1a</SP>O-[(PO)<SB>m</SB>/(EO)<SB>n</SB>]SO<SB>3</SB>M (1). In the formula, R<SP>1a</SP>is an 8-18C alkyl group; PO and EO are a propyleneoxy group and an ethyleneoxy group, respectively; m and n are each an average added molar number and are a numerical number satisfying 0<m<20 and 0≤n<20, respectively; PO and EO may be arranged at random or in blocks; and M is a cation. <P>COPYRIGHT: (C)2009,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.

  Conventionally, in order to increase the bleaching power of oxygen-based bleaching agents such as sodium percarbonate and sodium perborate, it has been proposed to use various bleaching activators in combination. In that case, it is also known that the bleach activator is used as a granulated product. However, granulated products containing bleach activators generally tend to be difficult to dissolve in water, so bleach activator granulations with excellent water solubility even under low temperature, low agitation power or submerged bleaching conditions. Development of things is required.

Patent Document 1 discloses a granulation method in which a mixture containing a bleach activator, a nonionic surfactant, and the like is mixed, and then the resulting mixture is extruded from an aperture screen.
Japanese Patent Publication No. 5-440

  In order to save water and save electricity, recent fully automatic washing machines are mainly used for washing conditions with lower bath ratio, lower agitation, and shorter time compared to conventional washing machines (drum-type washing). Machine). In addition, more clothes than the recommended clothing amount of the washing machine manufacturer are often washed (stuffed and washed). In these situations, rapid solubility in the bleach activator granulate is desired. In addition, it is desired that the granulated product has good characteristics without aggregation and the like during storage. In order to improve the physical properties of the granulated product, granulation is performed by adding a surfactant to the bleach activator. For example, an alkyl sulfate is used to improve the granulation property, but the solubility in water decreases. On the other hand, when polyethylene glycol alkyl ether sulfate is used instead of alkyl sulfate, solubility in water is improved, but granulation property is lowered. Even in the granulated product obtained by the method of Patent Document 1, there are cases where the bleach activator contained therein cannot sufficiently bring out the bleaching function from the viewpoint of achieving both granulation properties and solubility. It was. For this reason, there is a demand for a granulated activator bleaching product that is free from solidification and the like, has good granulation properties, and is superior in solubility, for example, solubility at low temperatures.

  As a result of diligent research to solve the above problems, the inventors of the present invention incorporated the compound having a specific structure into the bleach activator granulated product, thereby improving the granulation property of the bleach activator granulated product. It has been found that the solubility of the bleach activator granulated product is improved without lowering, and as a result, the organic peracid production rate and the bleaching performance are also improved.

The present invention is a granulated product of bleach activator comprising (a) component: bleach activator, and (b) component: compound represented by the following general formula (1).
^{R 1a O - [(PO)} m / (EO) n] SO 3 M (1)
(In the formula, R ^1a is an alkyl group having 8 to 18 carbon atoms, PO and EO are a propyleneoxy group and an ethyleneoxy group, respectively, m and n are average added mole numbers, and each independently represents 0 < (m <10, 0 ≦ n <20, PO and EO may be random or block, and M is a cation.)

  Moreover, this invention relates to the bleaching agent composition containing the said bleaching activator granulated material of this invention, and an inorganic peroxide.

  Moreover, this invention relates to the clothing bleaching method which makes the clothing contact the liquid composition containing 0.01-50 mass% of bleaching compositions of the said invention, and water.

Moreover, this invention is a manufacturing method of the bleaching activator granulation containing the following (a) component-(e) component, Comprising: (b) component, (c) component, (d) component are mixed previously Then, it relates to a method for producing a bleaching activator granulated product having a step of mixing the component (a) and the component (e).
Component (a): Bleach activator (b) Component: Compound represented by the following general formula (1) R ^1a O — [(PO) _m / (EO) _n ] SO ₃ M (1)
(In the formula, R ^1a is an alkyl group having 8 to 18 carbon atoms, PO and EO are a propyleneoxy group and an ethyleneoxy group, respectively, m and n are average added mole numbers, and each independently represents 0 < (m <10, 0 ≦ n <20, PO and EO may be random or block, and M is a cation.)
(C) Component: Nonionic surfactant (d) Component: One or more compounds selected from the group consisting of polyhydric alcohols and compounds represented by the following general formula (2), which are liquid at room temperature (25 ° C.) ^R2a- O-[(EO) _a / (PO) _b ] -H (2)
(In the formula, R ^2a 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 addition mole numbers, and each independently represents 0 to 0. The number is 10. However, a and b are not 0 at the same time.)
(E) Component: Binder material

  According to this invention, the bleaching activator granulated material excellent in solubility is obtained. Furthermore, when using a nonionic surfactant and a polyhydric alcohol 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 (2).
^{R 3a -C (= O) -LG} (3)
[Wherein, R ^3a 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 ^3b — (O) p —SO ₃ ^— and —O—R ^3b — (O) p —SO ₃ M (where R ^3b 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 ^3b preferably has 1 to 5 carbon atoms.

  The bleach activator in the present invention is not limited to the compound represented by the general formula (3), and conventionally used bleach activators can be used. For example, tetraacetylethylenediamine, glucose pentaacetate, tetraacetylglycoluril, alkanoyl or alkenoyl (the number of these groups is 8 to 14) oxybenzenecarboxylic acid or a salt thereof, alkanoyl or alkenoyl (the number of these groups is 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 a salt thereof 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 granulated product is preferably 10 to 95% by mass, more preferably 30 to 90% by mass from the viewpoint of bleaching performance.

<(B) component>
The bleaching activator granulated product of the present invention contains a compound represented by the following general formula (1) as the component (b).
^{R 1a O - [(PO)} m / (EO) n] SO 3 M (1)
(In the formula, R ^1a is an alkyl group having 8 to 18 carbon atoms, PO and EO are a propyleneoxy group and an ethyleneoxy group, respectively, m and n are average added mole numbers, and each independently represents 0 < (m <10, 0 ≦ n <20, PO and EO may be random or block, and M is a cation.)

In general formula (1), in order to obtain a high detergency, R ^1a is a linear alkyl group having 8 to 18 carbon atoms, and m is preferably 0.01 to 8, more preferably 0.8. 01 to 5, more preferably 0.01 to 3, more preferably 0.03 to 2, particularly preferably 0.03 to 0.8, and n is preferably 0.05 to 15, more preferably 0.1 to 10, especially 0.1 to 2 is preferred. In addition, PO and EO are preferably arranged in the form of a block copolymer, particularly those containing a block sequence in which PO is bonded to R ^1a O— and then EO is bonded, from the viewpoint of solubility.

  The content of the component (b) in the bleaching activator granulated product of the present invention is preferably 0.1 to 15% by mass, more preferably 0.1 to 10%, from the viewpoint of sufficient solubility and formulation. It is 0.2 mass%, More preferably, it is 0.2-7 mass%, Most preferably, it is 1-5 mass%. The component (b) is usually a mixture of compounds having different addition mole numbers of propyleneoxy groups and ethyleneoxy groups, and finally the average addition mole numbers m and n of the entire component (b) are those of the general formula (1). If it becomes a range, the addition mole number of the propyleneoxy group of each compound and an ethyleneoxy group will not ask | require. For example, as a result of using a compound containing no propyleneoxy group and ethyleneoxy group (alkyl sulfate ester salt) or a compound containing only ethyleneoxy group without containing propyleneoxy group (polyoxyethylene alkyl ether sulfate ester salt), The average added mole numbers m and n of the component (b) recognized by the general formula (1) may be within the range of the general formula (1).

  The mass ratio of the component (a) / component (b) is preferably 1000/1 to 1/3, more preferably 500/1 to 1/2, and particularly preferably 300/1, from the viewpoint of the caking property of the granulated product. ~ 1/2.

<(C) component>
The bleaching activator granulated product of the present invention may contain a nonionic surfactant as component (c) from the viewpoints of solubility and granulated physical properties. The nonionic surfactant of the present invention includes a nonionic surfactant obtained by adding an alkylene oxide to an alcohol, particularly a nonionic surfactant represented by the following general formula (3).
^R4a- O-[(EO) _c / (PO) _d ] -H (4)
[Wherein, R ^4a 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 the average number of moles added and is a number from 0 to 20, d is the average number of moles added and is a number from 0 to 20, except when both c and d are 0 at the same time. ]

  In general formula (4), 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 (4), 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.)], There is Emalgen LS-106 manufactured by Kao Corp. [EO adduct of C12 alcohol, 2.5 mol PO, 1.5 mol, EO3 mol adduct (melting point: -9 ° C)]. 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%.

<(D) component>
The granulated product of the bleach activator of the present invention is a compound that is liquid at room temperature (25 ° C.) selected from the group consisting of a polyhydric alcohol and a compound represented by the following general formula (2) as component (d). One or more may be contained.
^R2a- O-[(EO) _a / (PO) _b ] -H (2)
(In the formula, R ^2a 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 addition mole numbers, and each independently represents 0 to 0. The number is 10. However, a and b are not 0 at the same time.)

  For example, the component (d) 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.

  The compound represented by the general formula (2) 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 (2) 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 (2), 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 (d) from the viewpoint of solubility and physical properties of granules 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 (2), 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.

  As the component (d), for example, a commercially available product such as Japanese Pharmacopoeia glycerin manufactured by Kao Corporation can be used.

  The content of the component (d) 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.

<(E) component>
The bleaching activator granulated product of the present invention may contain a binder substance as the component (e). 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 1000 to 20000, more preferably 1000 to 10000, and more preferably 2000 to 6000, from the viewpoint of improving the granulation properties 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>
In addition to the component (a), the component (b), the component (c), the component (d), and the component (e), the bleach activator granule of the present invention is optionally added with other optional components, For example, a bleaching base, an enzyme, an inorganic salt such as sodium carbonate, a surfactant other than the component (b) and the component (c), a fluorescent agent, and the like can be blended. An example is shown below.

(1) Surfactant other than (b) component and (c) component The bleach activator granulated product of the present invention is an anionic surfactant as a surfactant other than (b) component and (c) component. One or more selected from cationic surfactants and amphoteric surfactants may be contained in an amount of 0 to 20% by mass, more preferably 1 to 15% by mass.

  Although the following can be considered as an example of the surfactant which can be contained, it is not limited to these.

  Examples of the anionic surfactant include alkylbenzene sulfonate, alkenyl ether sulfate, alkenyl sulfate, α-olefin sulfonate, saturated or unsaturated fatty acid salt, alkyl or alkenyl ether carboxylate, N-acyl amino acid type Surfactant, alkyl or alkenyl phosphate ester or a salt thereof can be used.

  In addition, a cationic surfactant such as a carboxybetaine type amphoteric surfactant, a sulfobetaine acid type amphoteric surfactant, an amino acid type amphoteric surfactant, an alkylamine oxide, and a quaternary ammonium salt may be blended.

(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 and the like fine powder 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 is obtained by blending the component (a) and the component (b), and 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), the component (d), and the component (e). For example, (a) component, (b) component, (c) component, (d) component, and (e) component are melt-mixed, and then the resulting mixture is granulated such as extrusion granulation. obtain.

  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) and one or more components selected from the component (c), the component (d), and the component (e). The said liquid substance may contain the component which is in the molten state by heating, and can also contain components other than (b) component, (c) component, (d) component, and (e) component.

  In particular, the bleach activator granulated product of the present invention has a step of previously mixing the component (b), the component (c), and the component (d), and then mixing the component (a) and the component (e). It is preferable to manufacture by a manufacturing method, (a) component, (b) component, (c) component, (d) The preliminary mixture (preferably liquid material) of a component is mixed first, and is in a molten state after that. (E) It is preferable to manufacture by the method of adding and mixing a component.

  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 NIPOWAL.

  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 viewpoint 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 agent 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 and cellulase is 1/50 to 1/1, preferably 1
/ 30 to 1/2 is preferable.

  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. Separately from the particles (III), they may be blended later or in the bleaching activator granulated product (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.

  The method for using the bleaching composition of the present invention is a liquid composition containing 0.01 to 50% by weight, preferably 0.01 to 30% by weight, more preferably 0.02 to 10% by weight and water. It is preferable to use it through a step of bringing an object into contact with clothing.

  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>
In Table 1, (a) component 9.1 kg, (b-1) component 1.04 kg, succinic acid [manufactured by Kawasaki Kasei Kogyo Co., Ltd.] 0.26 kg was mixed with a mixer (manufactured by Hosokawa Micron Co., Ltd .: Nauter mixer NX-S type ), Mixed and heated at a jacket temperature of 80 ° C, a rotation speed of 121 rpm, and a revolution speed of 5.5 rpm. When the temperature of the powder reached 60 ° C, it was previously melted at 70 ° C. (E) Component K- After adding 2.6 kg of PEG6000LA (manufactured by Kao Corporation) and 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.

<Examples 2-6 and Comparative Examples 1-3>
In the composition shown in Table 1, the same operation as in Example 1 was performed using each component so that the total amount of the mixture was 13 kg, and a bleaching activator granulated product was obtained.

<Example 7>
In Table 2, (b-1) component 0.39 kg, (c) component nonionic surfactant Emulgen KS-108 [manufactured by Kao Corporation] 0.26 kg, (a) component 9.1 kg, negative Charge 1.56 kg of ionic surfactant 2 and 0.26 kg of succinic acid (manufactured by Kawasaki Kasei Kogyo Co., Ltd.) 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, and 1.43 kg of component K-PEG6000LA (manufactured by Kao Corporation) melted at 70 ° C in advance 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.

<Examples 8 to 12>
In the composition shown in Table 2, the same operation as in Example 7 was performed using each component so that the total amount of the mixture was 13 kg, and a bleaching activator granulated product was obtained.

<Example 13>
In Table 2, (b-1) component 0.26 kg, (c) nonionic surfactant (manufactured by Kao Corporation: Emulgen KS-108) 0.26 kg, (d) ingredient glycerin (manufactured by Kao Corporation: Japan Bureau) 1) Mixer (Hosokawa Micron Co., Ltd.), 0.13 kg pre-mixed, (a) component 9.1 kg, anionic surfactant 2 1.56 kg, succinic acid (Kawasaki Chemical Industry Co., Ltd.) 0.26 kg ： Nauter 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. 1.43 kg of melted component (e) component K-PEG6000LA [manufactured by Kao Corporation] 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.

<Examples 14 to 18 and Comparative Examples 4 to 7>
In the composition shown in Table 2, the same operation as in Example 13 was performed using each component so that the total amount of the mixture was 13 kg, and a bleaching activator granulated product was obtained.

  The dissolution time of the bleaching activator granulated product obtained in Examples and Comparative Examples was evaluated by the following method. The results are shown in Tables 1 and 2.

<Dissolution time (T-90 dissolution time)>
Using 200 ml of ion-exchanged water with a water temperature of 10 ° C., add 1 g of the bleach activator granulated product obtained in the examples or comparative examples, and stir and mix with a magnetic stirrer (stirrer piece: 30 mm in length, 5 mm in diameter, rotating Number: 200 rpm), and the change in the electric conductivity of the 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. If the evaluation score is I or II, the form is good.
I ... There is no mass.
II… There is almost no lump, and the lump that is generated collapses to a granular shape when touched lightly.
III ... Many lumps occur.
IV: It hardens as a whole and there is a problem with handling.

<Granulation>
The mixing of each component with the composition of the above Example or Comparative Example was repeated 10 times with the same mixer, and the wall surface of the mixer and the attached state of the stirring blades were visually observed and judged according to the following criteria. If evaluation is A or B, it can be said that it is favorable granulation property.
A: Almost no adhesion on the wall of the mixer and the stirring blades B: A little adhesion on the wall of the mixer and the stirring blades C: Adherence to the wall of the mixer and the stirring blades is observed, and the deposits are easily Can't be removed

The components in the table are as follows.
Bleach activator: sodium dodecanoyloxybenzenesulfonate b-1: C ₁₂ H ₂₅ O (PO) _0.4 (EO) _1.5 SO ₃ Na (block adduct)
B-2: C ₁₂ H ₂₅ O (PO) ₃ (EO) ₅ SO ₃ Na (block adduct)
B-3: C ₁₂ H ₂₅ O [(PO) ₃ / (EO) ₅ ] SO ₃ Na (random adduct)
B-4: C ₁₂ H ₂₅ O (PO) ₈ (EO) ₁₂ SO ₃ Na (block adduct)
Anionic surfactant 1: C ₁₂ H ₂₅ O (EO) ₃ SO ₃ Na
- anionic surfactant 2: manufactured by Kao Corporation, Emal 10 powder, C ₁₂ H ₂₅ OSO ₃ represented by Na compounds, c: non-ionic surfactant, manufactured by Kao Corporation, Emulgen KS-108
D: Japanese glycerin glycerin, manufactured by Kao Corporation e: K-PEG-6000LA, manufactured by Kao Corporation, polyethylene glycol having a weight average molecular weight of 6000, a compound represented by HO- (EO) _n H

<Examples 19 to 22 and Comparative Examples 8 to 9>
Bleach compositions and bleach detergent compositions were prepared using some of the bleach activator granules obtained in Examples 1 to 18 and Comparative Examples 1 to 7, 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 2000 g linear alkyl (12 carbon atoms) benzenesulfonic acid soda, 500 g sodium lauryl sulfate, 300 g polyoxyethylene alkyl ether (Emulgen 510 manufactured by Kao Corporation), 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 A slurry was prepared, and the particles obtained by spray drying (drying temperature 190 ° C.) were put into a high speed mixer (FS-GC-10 type manufactured by Fukae Industry Co., Ltd.), and further polyoxyethylene lauryl ether (EO average addition mole) 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 3 below contains a bleach activator granulated product and an inorganic peroxide, and the bleaching detergent composition shown in Table 4 contains a bleach activator granulated product and an inorganic peroxide. And a surfactant-containing detergent particle. Regarding the bleaching composition shown in Table 3 and the bleaching detergent composition shown in Table 4, the organic peracid production rate and the bleaching performance (dipping conditions or washing conditions) were evaluated by the following methods.

<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. Thereafter, the bleaching agent composition obtained in Examples or Comparative Examples was added so that the bleaching activator granulated product was 0.05 g, stirred for 5 minutes, and 10 ml of 0.3% catalase aqueous solution was added. 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 calculated by the following equation.

<Bleaching performance (1): Soaking conditions>
The bleach composition was dissolved in 400 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 Nagatoen retort curry (Ampanman Curry, purchased in May 2007) with a mesh, the resulting liquid was heated until it was boiled. 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. Thereafter, 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. Washing conditions were as follows: washing time: 10 minutes, hardness: 4 ° DH, water temperature: 10 ° C., rinse: tap water in 5 minutes. The bleaching rate was calculated by the same method as above.

  From the comparison of the dissolution times of Examples 1 to 6 and Comparative Examples 1 to 3 in Table 1, it can be seen that the solubility of the granulated product is increased by adding the component (b). Further, from comparison between Examples 7 to 18 and Comparative Examples 4 to 7 in Table 2, the solubility is further increased by using a nonionic surfactant as the component (c) in combination with a polyhydric alcohol. I understand that.

  From the organic peracid production rate measurement results shown in Tables 3 and 4, the bleaching activator granules of Examples 13 and 16 containing the component (b) and the components (c) and (d) Compared to the granulated product of bleach activator, the organic peracid formation rate is high, and the bleaching performance evaluation results 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.

  Moreover, the bleaching activator granulated product of the present invention has improved solubility at low temperatures, and can improve the bleaching performance and reduce the unsettled residue of the bleach activator granulated product.

Claims (10)

(A) Component: Bleach activator, and (b) Component: Bleach activator granulated product containing the compound represented by the following general formula (1).
^{R 1a O - [(PO)} m / (EO) n] SO 3 M (1)
(In the formula, R ^1a is an alkyl group having 8 to 18 carbon atoms, PO and EO are a propyleneoxy group and an ethyleneoxy group, respectively, m and n are average added mole numbers, and each independently represents 0 < (m <10, 0 ≦ n <20, PO and EO may be random or block, and M is a cation.) The bleaching activator granulated product according to claim 1, further comprising (c) component: a nonionic surfactant. Furthermore, (d) component: One or more sorts of compounds which are liquid at normal temperature (25 ° C) chosen from the group which consists of a compound denoted by polyhydric alcohol and the following general formula (2) either The bleach activator granulated product according to claim 1.
^R2a- O-[(EO) _a / (PO) _b ] -H (2)
(In the formula, R ^2a 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 addition mole numbers, and each independently represents 0 to 0. The number is 10. However, a and b are not 0 at the same time.) Furthermore, (e) component: The bleaching activator granulated material of any one of Claims 1-3 containing a binder substance. (B) 0.1 to 15% by mass of component, (c) 0.1 to 10% by mass of component, (d) 1 to 10% by mass of component, (e) 1 to 30% by mass of component, The bleach activator granulated product according to claim 4. A bleaching agent composition comprising the bleaching activator granulated product according to any one of claims 1 to 5 and an inorganic peroxide. The bleach composition according to claim 6, further comprising surfactant-containing detergent particles. The bleach composition according to claim 6 or 7, which is for clothing. A method for bleaching clothing, comprising a step of bringing a liquid composition containing 0.01 to 50 mass% of the bleaching agent composition according to any one of claims 6 to 8 and water into contact with clothing. It is a manufacturing method of the bleaching activator granule containing the following (a) component-(e) component, Comprising: (b) component, (c) component, (d) component are mixed previously, (a) The manufacturing method of the bleaching activator granulation which has the process of mixing a component and (e) component.
Component (a): Bleach activator (b) Component: Compound represented by the following general formula (1) R ^1a O — [(PO) _m / (EO) _n ] SO ₃ M (1)
(In the formula, R ^1a is an alkyl group having 8 to 18 carbon atoms, PO and EO are a propyleneoxy group and an ethyleneoxy group, respectively, m and n are average added mole numbers, and each independently represents 0 < (m <10, 0 ≦ n <20, PO and EO may be random or block, and M is a cation.)
(C) Component: Nonionic surfactant (d) Component: One or more compounds selected from the group consisting of polyhydric alcohols and compounds represented by the following general formula (2), which are liquid at room temperature (25 ° C.) ^R2a- O-[(EO) _a / (PO) _b ] -H (2)
(In the formula, R ^2a 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 addition mole numbers, and each independently represents 0 to 0. The number is 10. However, a and b are not 0 at the same time.)
(E) Component: Binder material