JP3142382B2 - Method for producing granulated bleach activator and granulated bleach activator - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a bleaching activator granule excellent in solubility and storage stability, and to a bleaching activator granule.

[0002]

2. Description of the Related Art Various bleaching activators have been proposed for increasing the bleaching power of oxygen bleaching agents such as sodium percarbonate (hereinafter referred to as PC) and sodium perborate (hereinafter referred to as PB). . However, the function of the bleach activator is significantly impaired during storage due to interaction with oxygen-based bleach or other ingredients incorporated into the detergent. For this reason, the bleach activator must be protected from the surrounding environment by means such as granulation or surface coating. However, no protective measures should impair the dispersibility in the wash water.

[0003] Many studies have hitherto been made to satisfy such conditions. For example, JP-A-57-126899 ("Particulate bleach activator composition") discloses that a bleaching active ingredient is sprayed with a binder liquid in a bread granulator and then water-insoluble silica or silicate is sprayed. A method for obtaining a mass having good stability and high dispersibility is disclosed in JP-B-2-29719 ("Particulate bleach activator"). A method of obtaining a granulated product having good solubility by compressing and forming a dispersant by an extrusion granulator and then crushing and classifying the product is disclosed in JP-A-61-111400 ("Bleaching agent activator composition"). Discloses a method for obtaining activator granules obtained by spray-drying a bleaching activator and a water-soluble or inorganic hydratable substance. JP-A-57-192498 ("Bleaching granules, production method thereof and use in washing bleaching compositions") discloses an aqueous solution of sodium carboxymethylcellulose containing tetraacetylethylenediamine and an alkali metal polyphosphate as a binder. A granulation method is disclosed.

[0004]

The bleaching activator granules as described above have good storage stability of the granules alone, and under hot water washing conditions as in Europe and the United States. Dissolves relatively quickly in water. However, the dissolution rate is low and the function of the bleaching activator is slow when little stirring power is applied, such as under the washing condition of weak stirring with cold water as in many cases in Japan or under the bleaching condition of immersion. Can not be pulled out enough. Also, the bleaching activator granulated product is PC or P.
When blended with B, storage stability is not sufficient due to the reaction between PC or PB and the bleaching activator.

[0005] Accordingly, the present invention provides a high dissolution rate and a high level of bleach activator even under low-temperature, low-agitation washing conditions or under little-stirring conditions such as immersion bleaching conditions. It is an object of the present invention to obtain a bleaching activator granule having excellent storage stability even when the granules are mixed with PC or PB.

[0006]

As a result of various studies, the present inventors have found that PC or PB particles in which the inside and / or the surface of the particles are penetrated or coated with borate, or that the inside and the surface of the particles are penetrated. Alternatively, the core of the uncoated PB particles and the powder of the specific bleaching activator are granulated in the presence of a water-soluble organic binder, and, if necessary, further coated with a water-soluble polymer substance. As a result, they have found that the above problems can be solved, and have completed the present invention.

That is, the present invention relates to sodium percarbonate or sodium perborate in which the inside and / or the surface of the particles are infiltrated and / or coated with borate, or perborate in which the inside and / or the surface of the particles are not infiltrated or coated. Sodium acid core particles,
A powder of a bleach activator (excluding acetoxybenzenesulfonate) represented by the following general formula (I) or (II) is stirred and tumbled and granulated in the presence of a water-soluble organic binder to obtain a weight. An object of the present invention is to provide a method for producing a bleaching activator granulated material, wherein a granulated product having an average particle size (hereinafter, simply referred to as an average particle size) of 100 to 3000 μm is obtained.

[0008]

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[In the formula, R ¹ represents an optionally substituted straight-chain or branched carbon number of 1 to 22.
Or an unsubstituted or alkyl-substituted aryl group having 1 to 22 carbon atoms.

[0010]

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(R ² is H or an optionally substituted linear or branched alkyl or alkenyl group having 1 to 22 carbon atoms). Y: represents an optionally substituted alkylene group having 1 to 12 carbon atoms, an oxyalkylene group or a polyoxyalkylene group having 1 to 20 additional moles. n indicates a number of 0 or 1. L: a leaving group that reacts with hydrogen peroxide to generate an organic peracid. ]

[0012]

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Wherein R ^{3 is a} linear or branched alkyl group having 1 to 20 carbon atoms, an alkenyl group, a phenyl group, or an alkyl-substituted aryl group having 1 to 20 carbon atoms in the alkyl substituent. Is shown. R ^4, R ^5: the same or different and represent an alkyl group having 1 to 3 carbon atoms.

[0014]

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B: 1 to 1 carbon atoms which may have a branched chain
10 represents an alkylene group or -D- (OD) _p -group. here,
D represents the same or different alkylene group having 2 to 3 carbon atoms, and p represents a number having an average value of 0 to 10. m represents a number of 0 or 1. R ⁶ : an alkylene group having 1 to 12 carbon atoms which may be substituted or a formula

[0016]

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(Q and r are numbers from 0 to 2). L: a leaving group that reacts with hydrogen peroxide to generate an organic peracid. Z: inorganic or organic anionic group (however,

[0018]

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[0019] and L is if you make an intramolecular salt Z ^- in some cases without a) shows the. The present invention also relates to a method for heating or cooling after adding or mixing a water-soluble polymer substance, or adding or mixing a water-soluble polymer substance to the bleaching activator granules obtained by the above-mentioned production method, or A bleaching activator granule characterized in that a granulated product having an average particle diameter of 100 to 4000 μm surface-coated with a water-soluble polymer substance is obtained after adding or mixing an aqueous solution containing Is provided. The invention further relates to sodium percarbonate or sodium perborate in which the inside and / or the surface of the particles are infiltrated and / or coated with borate, or sodium perborate in which the inside and / or the surface of the particles are not permeated or covered. Average particle having a coating layer comprising 10 to 500 parts by weight of a bleaching activator represented by the above general formula (I) or 3 to 100 parts by weight of a water-soluble organic binder on a surface of 100 parts by weight of core particles. The present invention also provides a bleaching activator granule having a diameter of 100 to 3000 μm, and the present invention provides a water-soluble polymer substance having a surface area of 100 to 300 parts by weight of the bleaching activator granule.
Average particle size with 50 parts by weight of coating layer is 100 ~ 4000μm
And a bleaching activator granulated product.

The core particles used in the present invention may be PC or PB whose particles and / or the particle surface are infiltrated and / or surface-coated with borate, or PB which is not penetrated or coated on the inside and the surface of the particles. And average particle size is 50 ~ 3000μm
Is desirable. The narrower the particle size distribution, the better. When the average particle size is less than 50 μm, fine granules having a particle size of less than 100 μm increase and the granulation yield is poor. When the average particle size is more than 3000 μm, the solubility of the final granulated product deteriorates. Further, when PC which is not infiltrated or coated with borate is used, the storage stability is deteriorated, which is not suitable for the purpose of the present invention.

In the present invention, the borate used as the penetrating coating agent is preferably a sodium salt of boric acid, and more preferably sodium metaborate. The osmotic coating can also include sequestering agents such as ethylenediaminetetraacetate, nitrilotriacetate, phosphate, and the like. Further, inorganic salts such as silicates and sulfates may be included. The amount of borate required for osmotic coating is preferably 0.5 to 10% by weight, more preferably 2 to 8% by weight, based on PC or PB.

Stable PC or PB can be obtained by mixing PC or PB particles and an aqueous solution of borate in a solid-liquid state and then drying. Concentration of borate solution is 20-70% by weight
It is desirable that Further, in order to obtain PC or PB particles whose inside and surface are permeated with borate, the solid-liquid mixing temperature is adjusted according to the properties of the PC or PB particles used, the type and concentration of the borate used. It is necessary to select it appropriately. The operation of solid-liquid mixing and then drying is 1
Stable PC or PB particles can be obtained even at the same time. However, the range of conditions under which stable PC or PB particles can be obtained in one operation is considerably narrow. Therefore, a method of repeating the solid-liquid mixing-drying operation two or more times, preferably two to three times, is industrially advantageous.

In the present invention, PC or PB is used as a nucleus for the following reason. (1) When water penetrates into the granules during dissolution, the dissolution rate of the core particles themselves is high, so that the water disintegrates from the core particles therein, and the dispersion or dissolution of the activator is accelerated. (2) The bleach activator used in the present invention exhibits a bleaching effect by reacting with an oxygen-based bleach (PC, PB, etc.), but granulation using a substance other than PC or PB as a core. When a bleach activator is used, a compound other than the bleaching active ingredient is accompanied by the bleach activator, so that when blending the bleach activator and PC or PB as a bleach product, the degree of freedom of composition is low. Become.

The bleach activator used in the present invention is a compound represented by the above general formula (I) or (II). However, acetoxybenzene sulfonate is excluded. In the present invention, examples of the substituent "optionally substituted" include a hydroxyl group and an alkoxy group. The leaving group L in the general formula (I) or (II) includes the following.

[0025]

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(Wherein, s and t are each —H, —SO
^{_{3 M, -COOM, -COOR 7,}} -OH, halogen atom, -OR ^7,
—R ⁷ , represents —N (R ⁷ ) ₃ .E. Where M is an alkali metal,
An alkaline earth metal, an ammonium salt, an alkanol ammonium salt or the negative charge itself, wherein R ⁷ is H,
20 alkyl group, alkenyl group, hydroxyalkyl _{group, - (C 2 H 4 O} ) 1-5 -H or - represents a _{(C 3 H 6 O) 1-5} -H. E
Represents an inorganic or organic anion. Further, s and t may be the same or different. )

[0027]

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(In the formula, R ⁸ and R ⁹ have the same meaning as R ⁷ and may be the same or different at the same time, but at least one is not H.)

[0029]

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(Wherein, R ⁷ has the same meaning as described above. F is an alkylene group having 1 to 9 carbon atoms which may have a hydroxyl group,-(C ₂ H ₄ O) _1-5 -C ₂ H ₄ — or — (C ₃ H ₆ O) _1-5 —C ₃ H ₆ —.) D) Alkanesulfonic acid represented by —O—F—SO ₃ M (where F and M are It has the same meaning as described above.) E) Polyglycol ester represented by —O (CH ₂ COO) _k H (where k represents a number of 1 to 10)

[0031]

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(In the formula, R ¹⁰ represents an alkyl group having 1 to 22 carbon atoms, an alkenyl group or a phenyl group which may be substituted.)

[0033]

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(Wherein, R ⁷ and F have the same meanings as described above.)

[0035]

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(In the formula, R ¹¹ represents R ⁷ or M.)

[0037]

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(Wherein R ⁷ has the same meaning as described above, and W is

[0039]

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-C≡N, -NO ₂ or -SO ₂ R ⁷ , which may be the same or different. )

[0041]

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(In the formula, R ¹² represents R ⁷ excluding H.) The above-mentioned general formula (I) or (II) used in the present invention.
The bleaching activator represented by the formula (1) preferably has a particle size of 0.5 to 200 μm, more preferably 2 to 100 μm. In the present invention, it is optional to provide a coating layer of a water-soluble polymer substance on the surface of the bleaching activator granule, but the bleaching activator granule can be combined with PC or PB by this coating layer. The storage stability when blended can be further improved.

Specific examples of the water-soluble organic binder used in the present invention include polyethylene glycol, polypropylene glycol, and a nonionic surfactant. 400 to 2 molecular weight as polyethylene glycol
Suitable in the range of 0,000, preferably 600 to 10,000. As nonionic surfactants, polyoxyethylene (ethylene oxide addition mole number = 3 to 300) alkyl
(C _8-22 ) ether, polyoxyethylene (ethylene oxide addition mole number = 10-300) alkyl (C _8-14 ) phenol ether, or nonionic surfactants commercially available under the trade names Pluronic and Tetronic Agents, fatty acid glycerides having 8 to 20 carbon atoms, and the like. Among these water-soluble organic binders, polyethylene glycol having a melting point of 20 to 80 ° C., polypropylene glycol, and a nonionic surfactant are more preferable. They do not melt at temperatures below 20 ° C and have tackiness or film forming properties at temperatures above 20 ° C. The product temperature during granulation is based on the thermal decomposition of the bleach activator.
Since it is not preferable to exceed 80 ° C, the water-soluble organic binder is preferably a substance having a melting point of 20 to 80 ° C, more preferably
Materials having a melting point of 30-70 ° C are used.

In the present invention, besides the bleaching activator represented by the general formula (I) or (II) and the water-soluble organic binder, known components which are usually added can be added. For example, anionic surfactants such as sulfonates and sulfates having an alkyl group having 8 to 22 carbon atoms, alkylbenzene sulfonates having an alkyl group having about 9 to 15 carbon atoms, and anionic surfactants having about 6 to 12 carbon atoms. Having a linear or branched alkyl group, a nonionic surfactant such as an ethylene oxide condensate of alkyl ethylene obtained by condensing 5 to 25 moles of ethylene oxide with an alkyl phenol, a re-staining inhibitor such as polyvinylpyrrolidone, A bleaching stabilizer such as sodium polyacrylate can be added. Also, magnesium sulfate known as a stabilizer of peroxide or peroxide adduct,
Magnesium salts such as magnesium silicate can also be used. Further, in order to further improve the storage stability of the granulated product of the bleaching activator, a solid or powdered acid can be added in addition to the above substances. Examples of such an acid include organic acids such as formic acid, propionic acid, citric acid, fumaric acid, and succinic acid; inorganic acids such as phosphoric acid and sodium sulfite; and zeolites exhibiting solid acidity.

The mixing ratio of the core particles, the bleaching activator and the water-soluble organic binder is 10 to 500 parts by weight, preferably 50 to 300 parts by weight, based on 100 parts by weight of the core particles. 3 to 100 parts by weight of organic binder, preferably 5 to 5 parts by weight
A range of 80 parts by weight is desirable. If the bleaching activator is less than 10 parts by weight, the bleaching performance is unfavorably low, while if it exceeds 500 parts by weight, part of the bleaching activator remains in the granulation system without being granulated, and a good granulated product is obtained. Can not be obtained. If the amount of the water-soluble organic binder is less than 3 parts by weight, the granulating properties are insufficient and not preferable. If the amount exceeds 100 parts by weight, kneading in the granulator becomes severe, and good granulating properties cannot be obtained and the granulation is not performed. Adhesion occurs on the wall in the granulator, which is not preferable.

Preferred examples of the water-soluble polymer used in the present invention include polysaccharides which may have a sulfate group such as pullulan, dextrin, alkali metal alginate, hydroxypropylcellulose, hydroxypropylmethylcellulose, and the like. Polysaccharides having a hydroxyalkyl group or a carboxyalkyl group such as sodium carboxymethylcellulose, methylcellulose, polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol and the like can be mentioned. Among these, more preferred water-soluble polymer substances include hydroxypropyl methylcellulose or polyvinyl alcohol. The mixing ratio of the bleach activator granules and the water-soluble polymer substance is
The range of 0.5 to 50 parts by weight, preferably 1 to 30 parts by weight of the water-soluble polymer substance is desirably based on 100 parts by weight of the granulated material. When the amount of the water-soluble polymer substance is less than 0.5 part by weight, it is insufficient to cover the entire surface of the bleaching activator granule.

In the production of granules in the present invention, it is easy to control the particle size at the time of production and to make the granules easy, and the obtained granules are easily disintegrated or dissolved in the solution. Dry granulation by tumbling granulation. Examples of the agitating tumbling granulator include a Henschel mixer (manufactured by Mitsui Miike Kakoki),
High-speed mixer (manufactured by Fukae Kogyo Co., Ltd.), vertical granulator (manufactured by Powrex Corporation) and the like. These agitating tumbling granulators have a vertical stirring shaft with stirring blades installed inside a vertical mixing tank, but a Loedige mixer (horizontal type granulator having a horizontal stirring shaft). Redige Co., Germany) can be used as well. The core particles, the water-soluble organic binder, and the bleaching activator are charged into these granulators, and are stirred and mixed while flowing a heating medium such as hot water into the jacket of the granulator. When the raw material temperature in the granulator exceeds the melting point of the water-soluble organic binder,
Granulation starts around the core particles, but is tumbled on the surface of the stirring blade to form spherical particles. The water-soluble organic binder and the bleach activator may be added little by little during granulation. The particle size of the granulated product of the present invention is preferably from 100 to 3000 μm in consideration of solubility in water and handleability. After granulation, use a sieve or sizing machine as necessary
100 to 3000 μm, preferably 200 to 1500 μm particles
You may adjust so that it may become more than weight%.

The method for coating the surface of the bleaching activator granules with the water-soluble polymer substance in the present invention is not particularly limited, and the following methods are exemplified. A method in which a water-soluble polymer substance or an aqueous solution containing a water-soluble polymer substance is added to the bleach activator granules at a time, and then heated or dried. A method of heating or drying while adding a water-soluble polymer substance or an aqueous solution containing the water-soluble polymer substance to the bleaching activator granules in portions. Melt of water-soluble polymer substance into bleach activator granules,
Alternatively, a method of cooling or drying while spraying an aqueous solution containing a water-soluble polymer substance.

In order to obtain a better coating layer, the method of drying while spraying an aqueous solution containing a water-soluble polymer substance on the bleaching activator granules is particularly preferable. Apparatuses preferably used for surface coating include fluidized bed coating apparatuses such as Spiral Flow (manufactured by Freund Corporation), multiprocessors (manufactured by Powrex Corporation), and Aqua Coater (manufactured by Freund Corporation). Made),
A pan coating apparatus such as Doria Coater (manufactured by Powrex) may be used. As an example of a specific method, for example, when using a pan coating apparatus, a granulated substance containing a bleach activator is put into this apparatus, and hot air is flowed while rotating the coating pan. At the same time, the spraying can be carried out by spraying an aqueous solution containing a water-soluble polymer substance from a nozzle of a spray gun at an appropriate speed and then drying. At this time, talc,
Precipitated calcium carbonate and titanium dioxide can also be added. The particle size of the granulated material whose surface is coated with a water-soluble polymer substance is 100 to 100, taking into account the solubility in water.
4000 μm is preferred.

[0050]

EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

Example 1 4.0 kg of PC (water 0.5%, average particle diameter 495 μm) (material temperature 20
° C) with a stirrer-type mixer [High-speed mixer FS-GC-10
Mold; manufactured by Fukae Kogyo Co., Ltd.], and while stirring at 300 rpm, 0.35 kg of a 60% by weight aqueous solution of sodium metaborate / tetrahydrate (liquid temperature: 70 ° C.) was added dropwise over 3 minutes, followed by mixing for 1 minute. (At this time, water at 20 ° C. was flowed through the jacket). Next, this was transferred to a fluidized tank (SFC-15; manufactured by Freund Corporation), dried with hot air at 75 ° C for 10 minutes, and dried with cold air at 20 ° C.
Cool for minutes. Next, this was returned to the stirring mixer again,
The above operation was repeated. At this time, the amount of a 60% by weight aqueous solution of sodium metaborate tetrahydrate was 0.21 kg. 2.7 kg of a PC having an average particle diameter of 500 μm, in which the inside and the surface of the particles thus obtained were coated with sodium metaborate, were obtained by the following formula (III)

[0052]

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1.9 kg of the bleaching activator and 0.4 kg of polyethylene glycol (PEG6000) represented by the following formula, a total of 5 kg, were stirred by a rolling granulator [manufactured by Fukae Kogyo Co., Ltd .; high speed mixer FS-GC-10]. Mold), the jacket temperature is 70 ° C, the spindle speed is 300 rpm, and the chopper speed is 1700 rpm.
Granulated for minutes. After granulation, cool water (15 ℃) in jacket
And cooled the granulated material. After the temperature of the granulated material became 40 ° C. or less, the granulated material was sieved to obtain a product having a particle size of 350 to 1000 μm (weight average particle size 480 μm). At this time, the yield of the product based on the granulated product was 98%.

Example 2 4.5 kg of the granulated bleaching activator obtained in Example 1 was applied to a pan coating apparatus [DRC-500, manufactured by Freund Corporation].
And the coating pan was rotated at 20 rpm while flowing hot air at 65 ° C. at a flow rate of 3.5 m ³ / min. Powder temperature is 35
When the temperature reached ° C, a 10% by weight aqueous solution of hydroxypropylmethylcellulose was sprayed at a rate of 20 g / min. After spraying for 70 minutes, stop spraying, lower the hot air temperature to 50 ° C, and
Dried for 10 minutes. After that, cooling is performed by flowing cooling air at 20 ° C. When the powder temperature becomes 30 ° C. or less, the surface-coated granules are sieved to a particle size of 350 to 1000 μm (weight average particle size 500
μm) was used as the product.

Example 3 1.8 kg of PB having a weight average particle size of 500 μm was placed in a stirring and rolling granulator [Fukae Kogyo Co., Ltd .: High Speed Mixer FS-GC-10].
, Jacket temperature 70 ℃, spindle speed 300rpm,
When the chopper rotation speed is 1700 rpm and the temperature of the PB reaches 60 ° C., the following equation (IV)

[0056]

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2.8 kg of sodium n-nonanoyloxybenzenesulfonate represented by the following formula and polyethylene glycol
(PEG6000) 0.4 kg of the mixture was metered at a rate of 0.60 kg / Hr. After the supply is completed, cool water (15 ℃) in the jacket
And cooled the granulated material. After the temperature of the granulated material became 40 ° C. or less, the granulated material was sieved to obtain a product having a particle size of 350 to 1000 μm (weight average particle size 480 μm). At this time, the yield of the product based on the granulated product was 90%.

Example 4 500 g of the bleaching activator granules obtained in Example 3 were charged into a fluidized bed coating apparatus (manufactured by Powrex Co., Ltd., trade name: Ero Coater, STREA-1 type) and heated at 65 ° C. Hot air was blown at an air volume of 1.0 m ³ / min. When the powder temperature reached 35 ° C., a 10% aqueous solution of polyvinyl alcohol was sprayed at a rate of 6 g / min. After spraying for 25 minutes, the spraying was stopped, the hot air temperature was lowered to 50 ° C., and drying was performed for about 10 minutes. After that, cooling is performed by flowing cooling air at 20 ° C, and when the powder temperature falls to 40 ° C or less, the surface-coated granules are sieved to obtain a product having a particle size of 350 to 1000 µm (weight average particle size 490 µm) as a product. did.

Comparative Example 1 A bleaching activator granulated product was obtained in the same manner as in Example 1, except that the core particles were made of PC whose inside and / or particle surface were not penetrated with borate.

Comparative Example 2 4.1 kg of sodium n-nonanoyloxybenzenesulfonate used in Example 3 and polyethylene glycol (PE
G6000) 0.9 kg and a total of 5 kg using a granulator [Matsuzaka Trading Co., Ltd.
Manufactured by Redige Mixer Model M-20), and heated for 15 minutes at a jacket temperature of 70 ° C. and a spindle rotation speed of 1000 rpm. This mixture is fed to a horizontal extrusion granulator [Fuji Paudal Co., Ltd.]
Extruded with a pelletizer double EXD-60 type, screen diameter 1.0 mm). 3.0 kg of this granulated product was subjected to a rotation speed of 600 rpm with a marmellaizer (manufactured by Fuji Paudal K.K .;
Granulated for minutes. Next, the granulated product is sieved and the particle size is reduced to 350 to
A product having a size of 1000 μm was used as a product.

Test Example 1 The granules obtained in Comparative Example 1 and the granules obtained in Examples 1 and 2 were evaluated for storage stability (activator residual ratio) and dissolution rate by the following methods. It was measured. Table 1 shows the results.
Shown in From Table 1, the effect of using a PC coated with borate on the inside and / or the surface of the particle as the core particle is clear.

[Storage stability] A bleach activator granule alone and a blended product in which the bleach activator granule and PC were mixed at a weight ratio of 1/1 were each 10 g in a 50 ml plastic container.
Store at 40 ° C. under 80% relative humidity for 2 weeks. The residual amount of the activator of the sample before and after storage was determined by the following titration method, and the residual ratio of the activator was calculated by the following formula.

[0063]

(Equation 1)

Titration method 150 ml of water at 20 ° C. was placed in a 200 ml beaker, and the available oxygen was 0.1 ml.
After dissolving sodium percarbonate to a concentration of 05%, a bleaching activator granulation or a mixture of the bleaching activator granulation and PC is added to a 0.04% pure activator content. 2
100 rpm using a mechanical stirrer with cm stirring blades
After stirring for 10 minutes, 5 ml of a 0.3% catalase solution is added, and the mixture is stirred for 1 minute. To this solution are added 10 ml of a 10% potassium iodide solution and 10 ml of a 20% sulfuric acid solution, and titration is performed with a 0.1N sodium thiosulfate solution.

[Dissolution time] 1000 ml of water at 20 ° C. is put into a 1000 ml beaker, and a conductivity meter is set therein. After charging 5 g of the bleaching activator granule, the electric conductivity was recorded on a chart while stirring and mixing at 300 rpm using a 2 cm mechanical stirrer with stirring blades, and the measurement was performed when the electric conductivity became constant. stop. The time required to reach a certain conductivity is defined as the dissolution time.

Test Example 2 The storage stability (activator residual ratio) of the granules obtained in Comparative Example 2 and the granules obtained in Examples 3 and 4 was determined in the same manner as in Test Example 1. And the dissolution rate was measured. Table 1 shows the results. From the results shown in Table 1, it is clear that the granules according to Comparative Example 2 are inferior in solubility to the present invention.

[0067]

[Table 1]

[0068]

According to the present invention, the dissolution rate is high and PC or PB can be obtained even under low-temperature, low-agitation washing conditions, or under almost no agitation such as under immersion bleaching conditions.
Even when blended together, it becomes possible to obtain a bleaching activator granule having excellent storage stability.

────────────────────────────────────────────────── (5) References JP-A-5-32998 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C11D 11/00 C11D 7/54 D06L 3 / 02

Claims (6)

(57) [Claims] 1. A sodium percarbonate or sodium perborate whose inside and / or surface is infiltrated and / or coated with borate, or a sodium perborate whose inside and / or surface is not penetrated or coated. The core particles and a powder of a bleaching activator (excluding acetoxybenzenesulfonate) represented by the following general formula (I) or (II) are stirred and tumbled in the presence of a water-soluble organic binder. By doing
A method for producing a granulated bleaching activator, characterized in that a granulated product having a weight average particle size of 100 to 3000 µm is obtained. Embedded image [Wherein, R ¹ : a linear or branched carbon number of 1 to 22 which may be substituted;
Or an unsubstituted or alkyl-substituted aryl group having 1 to 22 carbon atoms. Embedded image (R ² is H or an optionally substituted linear or branched alkyl or alkenyl group having 1 to 22 carbon atoms). Y: represents an optionally substituted alkylene group having 1 to 12 carbon atoms, an oxyalkylene group or a polyoxyalkylene group having 1 to 20 additional moles. n indicates a number of 0 or 1. L: a leaving group that reacts with hydrogen peroxide to generate an organic peracid. [Chemical formula 3] [Wherein, R ^{3 represents a} linear or branched alkyl group having 1 to 20 carbon atoms, an alkenyl group, a phenyl group, or an alkyl-substituted aryl group having a total carbon number of 1 to 20 alkyl substituents. R ^4, R ^5: the same or different and represent an alkyl group having 1 to 3 carbon atoms. Embedded image B: represents an alkylene group having 1 to 10 carbon atoms which may have a branched chain or a -D- (OD) _p -group. Here, D represents the same or different alkylene groups having 2 to 3 carbon atoms, and p represents a number having an average value of 0 to 10. m represents a number of 0 or 1. R ⁶ : an optionally substituted alkylene group having 1 to 12 carbon atoms or a formula: (Q and r are numbers from 0 to 2). L: a leaving group that reacts with hydrogen peroxide to generate an organic peracid. Z: inorganic or organic anionic group (however, And if L make an intramolecular salt Z ^- where some without) shows a. ] 2. The bleaching composition according to claim 1, wherein the water-soluble organic binder is one or a mixture of two or more kinds selected from the group consisting of polyethylene glycol having a melting point of 20 to 80 ° C., polyethylene glycol, and a nonionic surfactant. A method for producing an activator granule. 3. Heating or cooling after adding or mixing a water-soluble polymer substance to any one of the bleaching activator granules obtained by the production method according to claim 1 or Bleaching characterized by obtaining a granulated product having a weight average particle diameter of 100 to 4000 μm surface-coated with a water-soluble polymer by drying after adding or mixing an aqueous solution containing a water-soluble polymer. A method for producing an activator granule. 4. The water-soluble polymer substance may be a polysaccharide optionally having a sulfuric acid group, a polysaccharide having a hydroxyalkyl group, a polysaccharide having a carboxyalkyl group, methylcellulose, polyvinylpyrrolidone, polyvinyl alcohol and polyethylene glycol. 1 selected from the group consisting of
The method for producing a bleaching activator granule according to claim 3, which is a seed or a mixture of two or more kinds. 5. A sodium percarbonate or sodium perborate in which the inside and / or the surface of the particles are infiltrated and / or coated with borate, or a sodium perborate in which the inside and / or the surface of the particles are not permeated or covered. A weight average having a coating layer composed of 10 to 500 parts by weight of the bleaching activator represented by the formula (I) or (II) and 3 to 100 parts by weight of a water-soluble organic binder on the surface of 100 parts by weight of the core particles. Particle size 100-3000
Bleaching activator granules of μm. 6. The bleaching activator granulate 100 according to claim 5.
A granulated bleach activator having a weight-average particle diameter of 100 to 4000 μm, having a coating layer of 0.5 to 50 parts by weight of a water-soluble polymer substance on the surface of parts by weight.