JPH083593A - Method for producing bleach activator granule and bleach activator granule - Google Patents

Abstract

(57) [Summary] [Structure] A bleach activator is formed by compaction molding in the presence of water and / or a water-soluble binder, an anionic surfactant, and if necessary, a solid or powdery acid. Obtain a granulate. [Effect] Even when the mixture is hardly stirred under low temperature and weak agitation under washing conditions, or under bleaching conditions in which it is placed in a pickle, the dissolution rate is high and even when it is blended with sodium percarbonate or sodium perborate. It became possible to obtain a bleaching activator granule having excellent storage stability.

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 bleach activator granule having excellent solubility and storage stability, and a bleach activator granule.

[0002]

2. Description of the Related Art Conventionally, various bleach activators have been proposed to increase the bleaching power of oxygen-based bleaching agents such as sodium percarbonate (hereinafter referred to as PC) and sodium perborate (hereinafter referred to as PB). There is. However, the function of the bleach activator is
During storage, it is significantly impaired by the interaction with oxygen-based bleaching agents or other ingredients incorporated in detergents. Therefore, the bleach activator must be protected from the surrounding environment by means such as granulation or surface coating. However, no protective measure should impede the dispersion solubility in the wash water.

Many studies have hitherto been conducted to satisfy such conditions. For example, in JP-A-5-32998 (“Method for producing bleach activator granules and bleach activator granules”), PC or PB pre-coated with borate is used as core particles for bleach activation. A method of stirring and rolling granulation with a powder of an agent, and JP-A-57-126899 (“Granular bleach activator composition”) discloses that a binder solution is sprayed on a bleaching active ingredient in a bread granulator. Then, a method of spraying water-insoluble silica or silicate to obtain a lump having good stability and high dispersibility is also disclosed in Japanese Patent Publication No. 2-29719 (“Granular bleach activator”). A method for obtaining a granule having good solubility by compression-molding a bleach activator, an expansive solubilizing substance, and a dispersant with an extrusion granulator and then pulverizing and classifying is further disclosed in JP-A-61-111400.
Japanese Unexamined Patent Publication ("Bleach activator composition") discloses a method for obtaining activator granules by spray-drying a bleach activator and a water-soluble or inorganic hydratable substance. In addition, JP-A-57-19
Japanese Unexamined Patent Publication No. 2498 (“Bleacher Granules, Production Method Thereof and Use in Washing Bleach Composition”) discloses a method of granulating tetraacetylethylenediamine and an alkali metal polyphosphate with an aqueous solution of sodium carboxymethylcellulose as a binder. Has been done. Further, Japanese Patent Publication No. 5-440 (“detergent composition”) discloses a granulation method in which a bleach activator is mixed with an ethoxylated nonionic surfactant and the mixture is extruded through an opening screen.

[0004]

The bleach activator granules as described above have good storage stability when the granules are used alone, and under hot water washing conditions such as those performed in Europe and America, Dissolves in water relatively quickly. However, the ones described in JP-A-57-126899, JP-B-2-29719, JP-A-57-192498 and JP-B-5-440 are common in Japan. Under the condition that the stirring force is hardly applied, such as the washing condition of cold water and weak stirring, or the bleaching condition in which the pickling solution is left alone, the dissolution rate is slow and the function of the bleach activator cannot be sufficiently obtained. In addition, JP-A-5-32998
JP-A No. 61-111400 and JP-A No. 61-111400 disclose P when bleach activator granules are blended with PC or PB.
Storage stability is not sufficient due to the reaction of C or PB with the bleach activator.

Therefore, the present invention has a high dissolution rate and produces a bleaching activator even under conditions such as washing at low temperature under mild agitation, or under bleaching conditions in which it is left in a soak. It is an object of the present invention to obtain a bleach activator granulated product having excellent storage stability even when the granulated product and PC or PB are blended.

[0006]

As a result of various studies, the present inventors have found that a bleaching activator is added in the presence of water and / or a water-soluble binder and an anionic surfactant, or with a water and / or water-soluble binder. By compacting in the presence of an anionic surfactant and a solid or powdery acid, and further by surface coating with a water-soluble polymeric substance, if necessary,
The inventors have found that the above problems can be solved and completed the present invention.

That is, the present invention provides a method for producing a bleaching activator granule shown in the following (1) to (9) and a bleaching activator granule shown in the following (10) and (11). It is provided. (1) A method for producing a bleaching activator granule, which comprises compacting a bleaching activator in the presence of water and / or a water-soluble binder and an anionic surfactant. (2) A bleach activator granulated product characterized by being compacted in the presence of water and / or a water-soluble binder, an anionic surfactant and a solid or powdery acid. Production method. (3) The method for producing a bleach activator granule according to the above (1) or (2), wherein the water content in the total amount charged is 10% by weight or less. (4) The bleach activator, at least one of the anionic surfactant is a water slurry, (1) or
(2) A method for producing a bleach activator granule as described. (5) Bleach activator, at least one of the anionic surfactant is sprayed and dried while spraying and then compaction molding, the method for producing a bleach activator granule according to the above (4) . (6) The bleach activator according to (1), (2), (4) or (5) above, wherein the water content in the total amount charged is from 10 to 80% by weight and a drying step is included. Method of manufacturing granulated product.

(7) The method for producing a bleaching activator granule according to the above (1) to (6), which comprises compacting and further crushing. (8) A mixture of a bleach activator powder, water and / or a water-soluble binder and an anionic surfactant, or a bleach activator powder, water and / or a water-soluble binder and an anionic surfactant. A slender extrudate is formed by mechanically extruding a mixture consisting of a solid or powdery acid from an opening screen with a pore size of 500 to 5000 μm, and crushing it to bleach with a weight average particle size of 200 to 5000 μm. The above (1), (2) characterized by obtaining an activator granule
The method for producing a bleaching activator granule according to item (3) or (7).

(9) Heating or cooling after or after adding and mixing a water-soluble polymer substance to the bleaching activator granules obtained by the production method according to any one of (1) to (8) above. Or,
Alternatively, a bleach activator granule characterized by obtaining a granule surface-coated with a water-soluble polymer substance by adding or mixing an aqueous solution containing a water-soluble polymer substance and drying while adding or mixing. Production method.

(10) Bleach activator 10-95% by weight, water 0.2-
10% by weight and / or 0.3-40% by weight of water-soluble binder,
Contains 5 to 65% by weight of anionic surfactant and 0 to 40% by weight of solid or powdery acid, and has a weight average particle size of 200 to 50.
Bleach activator granules that are 00 μm. (11) Bleaching activity having a weight average particle diameter of 200 to 5000 μm, having a coating layer of 0.5 to 50 parts by weight of a water-soluble polymer on the surface of 100 parts by weight of the bleaching activator granule according to (10) above. Granulating agent.

The bleaching activator used in the present invention is represented by tetraacetylethylenediamine, glucose pentaacetate, tetraacetylglycoluril, and the following general formula (I), (II), (III) or (IV). A compound etc. are mentioned.

[0012]

[Chemical 7]

[In the formula, R ¹ represents an optionally substituted linear or branched alkyl group or alkenyl group having 1 to 22 carbon atoms, or an unsubstituted or alkyl substituted aryl group having 1 to 22 carbon atoms.

[0014]

Embedded image

(R ² is H or an optionally substituted linear or branched alkyl group or alkenyl group having 1 to 22 carbon atoms). Y: 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 the number of 0 or 1. L: represents a leaving group that reacts with hydrogen peroxide to form an organic peracid. ]

[0016]

[Chemical 9]

[Wherein R ^{3 represents a} linear or branched alkyl group or alkenyl group having 1 to 22 carbon atoms, a phenyl group, or an alkyl-substituted aryl group having 1 to 20 total carbon atoms in the alkyl substituents]. R ⁴ and R ^{5 are the} same or different and each represents an alkyl group having 1 to 3 carbon atoms.

[0018]

[Chemical 10]

(R ⁷ represents H or an optionally substituted linear or branched C 1 to C 22 alkyl or alkenyl group), which may be the same or different. Y ₁ and Y ₂ : an optionally substituted alkylene group having 1 to 12 carbon atoms, an oxyalkylene group or a polyoxyalkylene group having 1 to 20 additional moles, which may be the same or different. n and m: each represents a number of 0 or 1. R ⁶ : an optionally substituted alkylene group having 1 to 12 carbon atoms or a formula

[0020]

[Chemical 11]

A group represented by (q and r are numbers from 0 to 2) is shown. L: represents a leaving group that reacts with hydrogen peroxide to form an organic peracid. Z: inorganic or organic anionic group (however

[0022]

[Chemical 12]

[0023]

[Chemical 13]

[In the formula, R ^{8 to} R ^{11 are the} same or different and each represents an alkyl group having 1 to 3 carbon atoms. R ¹² , R ¹³ : an optionally substituted alkylene group having 1 to 20 carbon atoms or a formula

[0025]

Embedded image

[0026]

[Chemical 15]

(R ¹⁴ represents H or an optionally substituted linear or branched alkyl group or alkenyl group having 1 to 22 carbon atoms), which may be the same or different. Y _3, Y _4: an optionally substituted alkylene group having 1 to 12 carbon atoms, shows a polyoxyalkylene group of the oxyalkylene group or an addition molar number of 1 to 20, may be the same or different. i, j, k: Indicates the number of 0 or 1, respectively. L: represents a leaving group that reacts with hydrogen peroxide to form an organic peracid. Z: inorganic or organic anionic group (however

[0028]

Embedded image

[0029]

[Chemical 17]

[Wherein R ^{15 to} R ^{18 are the} same or different and represent an alkyl group having 1 to 3 carbon atoms]. R ^{19 to} R ²² : an alkylene group having 1 to 20 carbon atoms which may be substituted or may have a branched chain, or a formula

[0031]

Embedded image

[0032]

[Chemical 19]

(R ¹⁴ is H or an optionally substituted linear or branched alkyl group or alkenyl group having 1 to 22 carbon atoms). u: Indicates the number of 0 or 1. Z: Indicates an inorganic or organic anion group. In the present invention, examples of the substituent which may be “substituted” include a hydroxyl group and an alkoxy group. Examples of the leaving group L in the general formula (I), (II) or (III) include the following.

[0034]

Embedded image

(In the formula, s and t are -H and -SO, respectively.
₃ M, -COOM, -COOR ²³ , -OH, halogen atom, -OR ²³ ,
-R ^23, represents a _{^{-N (R 23) 3 · E}} . Here, M is an alkali metal, an alkaline earth metal, an ammonium salt, an alkanol ammonium salt or the negative charge itself, R ²³ is H, an alkyl group having 1 to 20 carbon atoms, an alkenyl group, a 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. )

[0036]

[Chemical 21]

(In the formula, R ²⁴ and R ²⁵ have the same meaning as R ²³ and may be the same or different at the same time, but at least one of them is not H.)

[0038]

[Chemical formula 22]

(In the formula, R ²³ has the same meaning as described above.
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 − is shown. ) D) poly alkanesulfonic acids (wherein represented by _{-O-F-SO 3 M,} F, M are the as defined above.) E) represented by -O (CH ₂ COO) _v H Glycol ester (wherein v represents a number from 1 to 10)

[0040]

[Chemical formula 23]

(In the formula, R ²⁶ represents an alkyl group having 1 to 22 carbon atoms, an alkenyl group or an optionally substituted phenyl group.)

[0042]

[Chemical formula 24]

[0043]

[Chemical 25]

[0044]

[Chemical formula 26]

[0045]

[Chemical 27]

(In the formula, R ²⁸ represents R ²³ excluding H, and R ²³ has the same meaning as described above.) The bleach activator used in the present invention has a particle size of 0.5 to 200. μ
m is desirable, and 2-100 μm is even more desirable. Among these bleach activators, tetraacetylethylenediamine, glucose pentaacetate, tetraacetylglycoluril, and compounds represented by the general formulas (I) and (II) are more preferable.

In the present invention, water and / or a water-soluble binder is used as the binder. Examples of the water-soluble binder include a water-soluble organic binder and a water-soluble inorganic binder. Examples of the water-soluble organic binder include water-soluble polymers and nonionic surfactants. Specific examples of the water-soluble polymer, polyethylene glycol, polypropylene glycol, carboxymethyl cellulose,
Examples thereof include polycarboxylic acid salts such as sodium polyacrylate. The molecular weight of polyethylene glycol and polypropylene glycol is 400 to 20,000, preferably 6
Those in the range of 00 to 10,000 are suitable. Nonionic surfactants include polyoxyethylene (ethylene oxide addition mole number = 3 to 300) alkyl (C _8-22 ) ether, polyoxyethylene (ethylene oxide addition mole number = 10 to 300) alkyl (C _{8- 14} ) Phenol ether, sucrose ester, alkyl glycoside, polyoxyethylene alkylamine,
Examples thereof include polyoxyethylene-polyoxypropylene glycol, fatty acid monoethanolamide, fatty acid diethanolamide, and fatty acid glyceride having 8 to 20 carbon atoms. Examples of the water-soluble inorganic binder include sodium silicate. Among these water-soluble binders, polyethylene glycol and polypropylene glycol having a melting point of 20 to 80 ° C are more preferable. These polyethylene glycols and polypropylene glycols do not melt at a temperature lower than 20 ° C, and have adhesiveness or film forming property at a temperature of 20 ° C or higher. The temperature of the granulated product at the time of granulation is not preferable when it exceeds 80 ° C. from the viewpoint of thermal decomposition of the bleaching activator, so the water-soluble organic binder is preferably a substance having a melting point of 20 to 80 ° C., more preferably Materials with a melting point of 30-70 ° C. are used. These water and water-soluble binders may be used alone or as a mixture of two or more kinds. In particular, sodium silicate is preferably dissolved in water first and then mixed with other powder components. When water is used as the binder, the bleach activator compacted product may be dried in order to suppress hydrolysis of the bleach activator during storage.

In the present invention, the solubility of the bleach activator granules in water is improved, and the bleach activator and PC are added.
Alternatively, an anionic surfactant is used to accelerate the production of peracid by the reaction with PB or the like. Specific examples of the anionic surfactant used in the present invention include alkylbenzene sulfonate, alkyl or alkenyl ether sulfate, alkyl or alkenyl sulfate, olefin sulfonate, alkane sulfonate, higher fatty acid salt, α -Sulfo fatty acid salts or esters, alkyl or alkenyl ether carboxylates, and the like. Particularly preferred are alkylbenzene sulfonates having an alkyl group with 5 to 15 carbon atoms, alkyl ether sulfates and alkyl sulfates.

Further, in the present invention, a solid or powdery acid is used in order to further improve the storage stability of the bleach activator granulated product. Examples of such an acid include:
Examples thereof 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 showing solid acidity. Particularly preferred acids include fumaric acid, succinic acid, and zeolite exhibiting solid acidity.

In the present invention, a bleach activator, water and / or
Alternatively, in addition to the water-soluble binder, the anionic surfactant, and the solid or powdery acid, known components that are usually added can be added. For example, anti-redeposition agents such as polyvinylpyrrolidone, dissolution promoters such as urea, urea derivatives, thiourea, paratoluene sulfonate, and water-soluble inorganic salts, and bleach stabilizers such as sodium polyacrylate. Can be added. Further, known magnesium salts such as magnesium sulfate and magnesium silicate can be used as a stabilizer of peroxide or peroxide adduct.

Bleach activator of the present invention The blending ratio of the bleach activator, water and / or water-soluble binder, anionic surfactant, and solid or powdery acid in the granulated product is the bleach activator. Is 10-95% by weight, preferably 20-80% by weight, more preferably 30-70% by weight, water is 0.2-10% by weight, preferably 0.2-5% by weight, water-soluble binder is 0.3-40% by weight, Preferably 0.3 to 30% by weight, more preferably 0.3 to
20% by weight (however, one or both of water and water-soluble binder can be used), anionic surfactant is 5 to 65% by weight, preferably 10 to 50% by weight, more preferably 15 to 45% by weight. %, Solid or powdered acid 0-40% by weight,
Preferably 0 to 30% by weight, more preferably 0 to 20% by weight
The range of is desirable. If the bleach activator is less than 10% by weight,
Since the proportion of the bleaching activator in the granulated product is small, the amount of the granulated product added in order to exhibit sufficient bleaching performance is not preferable, while if it exceeds 95% by weight, the bleaching activator is not preferable. A part of the above remains as a fine powder in the granulation system without being granulated, and a good granulated product cannot be obtained. Exceeding 10% by weight of water accelerates the decomposition of the bleaching activator, which is not preferable.
When the content of the water-soluble binder is more than 40% by weight, the kneading in the granulator becomes vigorous, good granulation properties cannot be obtained, and the wall inside the granulator adheres, which is not preferable. If the amount of water or the water-soluble binder is less than the above amount, consolidation molding is unsatisfactory, which is not preferable. Regarding the use ratio of water and the water-soluble binder, it is preferable to use water rather than the water-soluble binder, since the amount used can be smaller, so that the ratio of the bleach activator in the bleach activator granulated product can be increased. . However, since the bleaching activator is easily hydrolyzed by adding water, the ratio of water to the water-soluble binder used is
It needs to be changed depending on the ease of hydrolysis of the bleach activator. When water and a water-soluble binder are used in combination, the amount of the water-soluble binder used is smaller than when used alone, and the strength of the consolidated molded product is increased as compared with the case where water is used alone. Is especially preferred. Further, if the amount of the anionic surfactant is less than 5% by weight, the solubility promoting effect is small, and if it exceeds 65% by weight, the solubility promoting effect is great, but the storage stability during storage is deteriorated, which is not preferable. When the solid or powdery acid content exceeds 40% by weight, the improvement of storage stability during storage is not increased, which is not preferable.

In the present invention, it is optional to provide a coating layer of a water-soluble polymer on the surface of the bleaching activator granule. Alternatively, the storage stability when blended with PB can be further improved. Preferred examples of the water-soluble polymer substance used in the present invention include pullulan, dextrin, polysaccharides which may have a sulfuric acid group such as alkali metal alginate, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, hydroxypropyl ethyl cellulose. ,
Polysaccharides having hydroxyalkyl group or carboxyalkyl group such as sodium carboxymethyl cellulose,
Examples include methyl cellulose, polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol and the like. Among these, more preferable water-soluble polymer substances include hydroxypropylmethylcellulose, hydroxypropylethylcellulose and polyvinyl alcohol.

In the present invention, the blending ratio of the bleach activator granules and the water-soluble polymer substance is 0.5 to 50 parts by weight, preferably 1 to 100 parts by weight of the granules.
A range of 30 parts by weight is desirable. If the amount of the water-soluble polymer is less than 0.5 part by weight, it is insufficient to cover the entire surface of the granulated bleach activator, while if it exceeds 50 parts by weight, the solubility in water is deteriorated, which is not preferable.

In producing the granulated product in the present invention, the obtained granulated product is granulated by a compaction molding method in which the granulated product is easily disintegrated or dissolved in a solution. The consolidation molding method is not particularly limited, and the diameter is 500 to 5000 μm by an extrusion granulator, preferably
A method of forming a cylindrical compacted body of 500 to 3000 μm, a method of compacting between two rotating rolls to form a plate-shaped compacted body having a thickness of 200 to 10,000 μm, preferably 500 to 5000 μm,
500 to 10,000 μm diameter, preferably 500 depending on briquette machine
A method of forming a tablet-shaped compact having a diameter of up to 5000 μm can be used.

As an extrusion granulator, Fuji Paudal Co., Ltd.
Examples include pelletizer double manufactured by Kikusui Co., Ltd., and briquette manufactured by Shinto Kogyo Co., Ltd., tableting machine manufactured by Kikusui Co., Ltd., and the like. Among these, the method of consolidating with an extrusion granulator is more preferable from the viewpoint of good solubility and fluidity of the granulated product and excellent productivity. The pore size of the screen of the extrusion granulator is preferably 500 to 5000 μm, and particularly preferably 500 to 3000 μm in order to efficiently produce a granular granulated product having a weight average particle size of 200 to 5000 μm.

In the present invention, as described above, the total amount of the bleaching activator, anionic surfactant, water and / or water-soluble binder, solid or powdery acid, and known components usually added is added. The bleaching activator having a water content of 10% by weight or less may be compacted in the presence of water and / or a water-soluble binder and an anionic surfactant. In order to further improve the solubility, the bleaching activator, and / or the water concentration of the anionic surfactant is used, or the water concentration is adjusted to 10 to 80% by weight by adding water. You may adjust to%. It is considered that this operation makes it possible to improve the solubility of the granulated product because the bleaching activator and the anionic surfactant are brought into close contact with each other in the granulated product using water as a medium. Moisture concentration in the total amount charged
If it is less than 10% by weight, there is no effect of improving the solubility,
If it exceeds 80% by weight, the load during drying increases. A bleach activator, an anionic surfactant, water and / or a water-soluble binder, a solid or powdery acid, and a water concentration of 10 to 80% by weight in the total amount of known components that are usually added. Is dried so that the water content in the total charge is 10% by weight or less before compaction molding, or the blending ratio of water in the bleach activator granules is 10% by weight or less after compaction molding. There is a need. When the water content after drying exceeds 10% by weight, decomposition of the bleaching activator is promoted, which is not preferable. The drying method is not particularly limited, but the following methods are available.

Bleach activator, anionic surfactant,
A method in which water and / or a water-soluble binder and the like are added all at once and then dried by heating and / or reduced pressure. A method in which powder or solid containing at least one of a bleaching activator and an anionic surfactant is dried under heating and / or reduced pressure while adding other components containing water in portions. A method in which a bleach activator, an anionic surfactant, water and / or a water-soluble binder, etc., and commonly known components are compacted, and then fluidized and dried with heated air.

Examples of the apparatus used for drying include a batch kneader [manufactured by Fuji Paudal Co., Ltd.], a continuous kneader [manufactured by Kurimoto Iron Works Co., Ltd.], a universal mixing stirrer [manufactured by Dalton Co., Ltd.] and the like. There are fluid-drying devices such as a decompression type kneader, a vibration drying cooling device (manufactured by Shinko Electric Co., Ltd.), and a continuous fluidized bed dryer (manufactured by Nara Machinery Co., Ltd.).
When at least one of the bleaching activator and the anionic surfactant is in a water slurry state, it is possible to dry while spraying the water slurry. As a spray dryer,
A fluidized bed dryer such as Spiral Flow [manufactured by Freund Industrial Co., Ltd.] or multiprocessor [manufactured by Powrex Co., Ltd.] can be used. The drying temperature is 30 to 150 ° C, preferably 40 to 100 ° C. If it is lower than 30 ° C, the drying efficiency is poor, and if it is higher than 150 ° C, it is not preferable in terms of decomposition of the bleach activator.

When water is not used as a binder, the temperature at the time of consolidation is near the melting point of the binder, more preferably 20 ° C. above the melting point of the binder, in order to suppress generation of fine powder and to impart appropriate particle strength. It is preferable to perform consolidation in the range of high temperature to 5 ° C. lower temperature. If the compaction temperature is too low, the compaction will not be sufficiently carried out and the amount of fine powder will increase, and if the compaction temperature is too high, the solubility of the granulated product obtained by the compaction body becoming too hard will be lowered,
It is not preferable because the bleaching activator decomposes and the activity decreases. When water is used as the binder, the compaction molding temperature is 0 to 100 ° C, preferably 20 to 80 ° C. 0 ° C
If it is lower than the melting point of water, water is not effective as a binder, and if it is higher than 100 ° C, it becomes higher than the evaporation temperature of water.
In addition, the bleach activator may be decomposed, which is not preferable.

After compacting, if necessary, a crushing step is performed to adjust the particle size to a range of 200 to 5000 μm in weight average particle size, and a surface coating step is performed using a marumerizer to obtain a uniform coating layer. The step of spheroidizing the granulated product can also be included in the consolidation granulation step. The crushing method is not particularly limited, and a known crusher (or crusher) can be used, and examples thereof include Fitzmill (Fitzpatrick, USA), commuter (Fuji Paudal Co., Ltd.) and the like. The temperature supplied to the crusher is preferably cooled to around room temperature, for example, a compacted product produced by an extrusion granulator is supplied to an oscillating cooler, cooled to a predetermined temperature, and then crushed to crush the crushed product. Adhesion inside is suppressed. A granulated product having a weight average particle size of 200 to 5000 μm can be obtained by crushing, but the crushed product may be further classified in order to further reduce fine powder and coarse particles. If you perform classification operation,
Fine powder can be recycled to the mixing step, and coarse particles can be recycled to the crushing step for reuse.

The method of coating the surface of the bleach activator granules with the water-soluble polymer substance in the present invention is not particularly limited, and the following methods may be mentioned. A method in which a water-soluble polymer substance or an aqueous solution containing a water-soluble polymer substance is added all at once to a granulated bleach activator, and then heated or dried. A method of heating or drying while adding a water-soluble polymer substance or an aqueous solution containing a water-soluble polymer substance in divided portions to a bleach activator granule. Bleach activator granules melt of water-soluble polymer,
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 on the bleach activator granules is particularly preferable. As a device preferably used for surface coating, a fluidized bed coating device such as Spira Flow [manufactured by Freund Industrial Co., Ltd.], multiprocessor [manufactured by Powrex Co., Ltd.], or an aqua coater [Freund Industrial Co., Ltd.] Made],
A pan coating device such as a Doria coater (manufactured by Paulec Co., Ltd.) can be used. As an example of a specific method, when using a pan coating apparatus, for example, a granulated product containing a bleach activator is put into this apparatus, and hot air is flown while rotating the coating pan. At the same time, an aqueous solution containing a water-soluble polymer substance is sprayed from a nozzle of a spray gun at an appropriate speed, and then dried. At this time, talc, precipitated calcium carbonate, or titanium dioxide can be added as an anti-aggregation agent. Considering the solubility in water, the particle size of the granules surface-coated with a water-soluble polymer substance should be 200-200.
5000 μm is preferable.

[0063]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples. still,
In the examples,% is by weight unless otherwise specified.

Example 1 2.7 kg of a bleaching activator represented by the following formula (V), polyethylene glycol (molecular weight 6000, hereinafter abbreviated as PEG6000)
0.6 kg, sodium alkyl sulfate (carbon number of alkyl group is 1
2) 1.7kg, 5kg in total [Fukae Industry Co., Ltd .:
High-speed mixer FS-GC-10 type], jacket temperature 80 ℃, spindle speed 200rpm, speed of crushing blade
The mixture was mixed and heated at 1500 rpm, and the mixture was extracted when the powder temperature reached 70 ° C. Then, the obtained mixture was extruded and granulated (by Fuji Paudal Co., Ltd .: pelleter double E
XD-100 type) was extruded through a screen with a pore size of 800 μm for consolidation. The obtained extrudate is a vibration cooler (Fuji Powdal Co., Ltd .: vibro / flow dryer VDF
/ 6000 type) and then crushed with a particle sizer (Fuji Paudal Co., Ltd .: knife cutter FL-200 type). The obtained crushed material was classified by a classifier (Dekuju Seisakusho Co., Ltd .: Kotobuki type vibrating sieve), and a particle size of 350 to 1400 μm (weight average particle size 900 μm) was used as a bleach activator granulated product. did.

[0065]

[Chemical 28]

Example 2 A bleaching activator granule having a particle size of 350 to 1400 μm (weight average particle size 900 μm) was prepared in the same manner as in Example 1 except that 0.3 kg of powdered succinic acid was added to the raw material. Got

Example 3 Except that the screen of the extrusion granulator had a pore size of 500 μm,
The same operation as in Example 2 is performed to obtain a particle size of 350 to 1400 μm.
A bleaching activator granule having a (weight average particle diameter of 600 μm) was obtained.

Example 4 The bleaching activator represented by the formula (V) was used as the bleaching activator 60.
%, Alkyl (C ₁₂ ) sodium sulfate 5%, PEG6000 15%,
The same operation as in Example 3 was carried out except that 20% of powdery succinic acid was used, and the particle diameter was 350 to 1400 μm (weight average particle diameter 600 μm.
A bleach activator granule of m) was obtained.

Example 5 The bleaching activator represented by the formula (V) was blended with the bleaching activator 30.
%, Alkyl (C ₁₂ ) sodium sulfate 50%, PEG6000 10%,
The same operation as in Example 1 was performed except that the powdery succinic acid was 10%, and the particle size was 350 to 1400 μm (weight average particle size 900 μm.
A bleach activator granule of m) was obtained.

Example 6 A bleaching activator represented by the formula (V) 55
%, Alkyl (C ₁₂ ) sodium sulfate 37%, water 2%, powdered succinic acid 6%, bleaching with a particle size of 350 to 1400 μm (weight average particle size 900 μm) was performed in the same manner as in Example 1. An activator granule was obtained.

Example 7 The bleaching activator 53 represented by the formula (V) was blended with the raw materials.
%, Alkyl (C ₁₂₎ 35% sodium sulfate, PEG 6000 5%, 1% water, except that the 6% powdered succinic acid, particle size 350~1400μm Operations in the same manner as in Example 1 (weight average particle diameter
Granules of bleach activator (900 μm) were obtained.

Example 8 1.7 kg of raw material sodium alkyl sulfate was added to 1.7 kg of straight chain sodium alkylbenzene sulfonate (alkyl group having 12 to 13 carbon atoms).
The same operation as in Example 2 was carried out except that
A bleaching activator granule having a weight average particle diameter of 50 to 1400 μm (900 μm) was obtained.

Example 9 2.8 kg of bleach activator represented by the following formula (VI), PEG600
0 was 0.8 kg, alkyl (C ₁₂ ) sodium sulfate was 1.0 kg, powdered succinic acid was 0.4 kg, and a total of 5.0 kg was used, and the same operation as in Example 1 was carried out to obtain a particle diameter of 350 to 1400 μm (weight average particle diameter). Granules of bleach activator of 900 μm) were obtained.

[0074]

[Chemical 29]

Example 10 2.5 kg of tetraacetylethylenediamine (TAED), PE
1.0 kg of G6000, 0.5 kg of alkyl (C ₁₂ ) sodium sulfate,
Using 1.0 kg of powdered succinic acid and 5.0 kg in total, the same operation as in Example 1 was carried out to obtain a bleaching activator granule having a particle diameter of 350 to 1400 μm (weight average particle diameter 900 μm).

Example 11 The mixture obtained by mixing and raising the temperature in the same manner as in Example 1 was supplied to a briquette machine (manufactured by Shinto Kogyo Co., Ltd .: Brichetta BSS-201 type) to obtain a tablet shape having a weight average particle diameter of 3000 μm. The bleach activator granules of were obtained.

Example 12 A mixture obtained by mixing and raising the temperature in the same manner as in Example 2 was supplied to a briquette machine (manufactured by Shinto Kogyo Co., Ltd .: Briquetta BSS-201 type) to obtain a tablet shape having a weight average particle diameter of 3000 μm. The bleach activator granules of were obtained.

Example 13 The bleaching activator represented by the formula (V) was used as the bleaching activator 30.
%, Alkyl (C ₁₂ ) sodium sulfate 50%, PEG6000 10%,
The powdery succinic acid was 5% and granulated in the same manner as in Example 12 to obtain a tablet-shaped bleaching activator granulated product having a weight average particle diameter of 4000 μm.

Example 14 500 g of the bleaching activator granules obtained in Example 2 were charged in a fluidized bed coating apparatus [manufactured by Paulec Co., Ltd., trade name: Elocoater, STREA-1 type] at 65 ° C. Hot air 1.0 m ³ /
It was blown with a minute amount of air. From the time when the powder temperature reached 35 ° C., a 10% aqueous solution of hydroxypropylmethyl cellulose was sprayed at a rate of 5 g / min. After spraying for 30 minutes, spraying was stopped, the hot air temperature was lowered to 50 ° C., and drying was performed for about 10 minutes. Then 20 ° C
When the powder temperature falls below 30 ° C, the surface-coated granules are sieved to give a particle size of 350 ~ 14
A product having a size of 00 μm (weight average particle diameter of 950 μm) was used as a product.

Example 15 Glucose pentaacetate (2.7 kg) was added with solid content of sodium alkenyl ether sulfate (alkenyl group having 12 carbon atoms).
Prepared in a batch type kneader (manufactured by Fuji Paudal Co., Ltd.) with 5.7 kg of water slurry containing 30% by weight Jacket temperature 80
The mixture was mixed at a temperature of 50 ° C., a rotation speed of 50 rpm, and a vacuum degree of 50 Torr, and dried until the water content became 5% by weight. Then, the obtained mixture was extruded through a screen having a pore size of 800 μm by an extrusion granulator (manufactured by Fuji Paudal Co., Ltd .: Pelleter Double EXD-100 type) to be consolidated. The extrudate obtained is cooled with a vibration cooler (Fuji Paudal Co., Ltd .: Vibro / Flow Dryer VDF / 6000 type), and then a granulator (Fuji Paudal Co., Ltd .: knife cutter FL-200 type). ). The obtained crushed material is classified by a classifier (manufactured by Tokuju Manufacturing Co., Ltd.
A bleaching activator granulated product having a particle size of 350 to 1400 μm (weight average particle size of 900 μm) was classified by a circular vibrating screen.

Example 16 The same operation as in Example 15 was carried out except that 13.5 kg of a water slurry containing 20% by weight of glucose pentaacetate solids and 1.7 kg of sodium alkyl sulfate (alkyl group having 12 carbon atoms) were used. Performed particle size 350-1400μm (weight average particle size 9
A bleach activator granulation product of 00 μm) was obtained.

Example 17 13.5 kg of an aqueous slurry containing 20% by weight of glucose pentaacetate solids and 5.7 kg of an aqueous slurry containing 30% by weight of alkenyl ether sulfate sodium (alkenyl group having 12 carbon atoms) solids were used. Except for this, the same operation as in Example 15 is performed to obtain a particle size of 350 to 1400 μm (weight average particle size of 900 μ
A bleach activator granule of m) was obtained.

Example 18 Polypropylene glycol (molecular weight: 1000) was added as a raw material in an amount of 0.6.
The same operation as in Example 15 was carried out except that kg was added to obtain a bleaching activator granule having a particle diameter of 350 to 1400 μm (weight average particle diameter 900 μm).

Example 19 Fatty acid glyceride (having 12 carbon atoms in fatty acid) was used as a raw material in an amount of 0.6.
The same operation as in Example 16 was carried out except that kg was added to obtain a bleaching activator granule having a particle diameter of 350 to 1400 μm (weight average particle diameter 900 μm).

Example 20 Example 17 except that 0.6 kg of sodium silicate was added to the raw materials.
The same operation was performed to obtain a bleaching activator granule having a particle diameter of 350 to 1400 μm (weight average particle diameter 900 μm).

Example 21 Tetraacetylethylenediamine (TAED) powder 200 g
Was charged into a fluidized bed coating apparatus (manufactured by Paulec Co., Ltd., trade name: Elocoater, STREA-1 type), and hot air at 50 ° C was flown at a flow rate of 0.6 m ³ / min. Add 30 solids to this fluidized bed.
Sodium alkyl sulfate containing 1% by weight
2) Spraying 600g of water slurry while drying, the water content becomes 1
Continue until 0% by weight. Next, the obtained mixture is extruded and granulated (Fuji Paudal Co., Ltd .: Pelleter Double E)
XD-100 type) was extruded through a screen with a pore size of 800 μm for consolidation. The obtained extrudate is a vibration cooler (Fuji Powdal Co., Ltd .: vibro / flow dryer VDF
/ 6000 type) and then crushed with a particle sizer (Fuji Paudal Co., Ltd .: knife cutter FL-200 type). The obtained crushed material was classified by a classifier (Circular vibrating sieve manufactured by Tokuju Seisakusho Co., Ltd.), and a particle having a particle diameter of 350 to 1400 μm (weight average particle diameter 900 μm) was used as a bleach activator granulated product. .

Comparative Example 1 4.4 kg of the bleach activator represented by the above formula (V) and PEG600
0 0.6 kg, using a total of 5 kg, the same operation as in Example 1 was carried out to obtain a particle diameter of 350 to 1400 μm (weight average particle diameter of 900 μm).
A bleach activator granule of m) was obtained.

Test Example Regarding the granules obtained in Comparative Example 1 and the granules obtained in Examples 1 to 21, storage stability (bleach activator residual rate) and solubility ( The peracid production rate) was evaluated. The results are shown in Table 1, Table 2 and Table 3.

<Storage Stability> 10 g of each of the bleach activator granules alone and the compounded mixture of the bleach activator granules and PC in a weight ratio of 1/1 were put in a 50 ml plastic container.
Store for 4 weeks at 40 ° C and 80% relative humidity. The residual amount of the bleach activator of the sample before and after storage was determined by the following titration method, and the residual ratio of the bleach activator was calculated by the following formula.

[0090]

[Equation 1]

-Titration method- 150 ml of water at 20 ° C was placed in a 200 ml beaker, and available oxygen was reduced to 0.
After dissolving sodium percarbonate to be 05%, bleach activator granules or a mixture of bleach activator granules and PC were added so that the bleach activator content was 0.04%. Using a mechanical stirrer with a 2 cm stirring blade
After stirring at 100 rpm for 10 minutes, 0.3% catalase solution 5
Add ml and stir for 1 minute. To this solution, 10 ml of 10% potassium iodide solution and 10 ml of 20% sulfuric acid solution are added, and titration is performed with 0.1N sodium thiosulfate solution.

<Measurement method of peracid generation rate> Sodium percarbonate 0.3 g
And the following anionic detergent ¹⁾ 0.3 g of bleaching activator granules in a solution of 75 g of tap water, the bleaching activator being 1/16 equivalent to hydrogen peroxide in sodium percarbonate Dissolve so that the reaction mixture becomes 20% and react at 20 ° C for 3 minutes, add 2.5 ml of 0.3% catalase solution and stir for 1 minute.
% Potassium iodide solution is added and titrated with a 0.1 N sodium thiosulfate solution, and the peracid production rate is calculated by the following formula.

[0093]

[Equation 2]

Note) 1) Anionic detergent Linear alkylbenzene sulfonate sodium (carbon number 12 to 13) 25% Sodium alkyl sulfate (carbon number 14 to 15) 8% Sodium carbonate 20% Glauber's salt balance 2) Effective oxygen 13.5% Titration rate of 100% peracid generation when using sodium percarbonate

[0095]

[Table 1]

[0096]

[Table 2]

[0097]

[Table 3]

Note) * 1: V is a bleaching activator represented by the above formula (V), VI is a bleaching activator represented by the above formula (VI), TAED is tetraacetylethylenediamine, and GPA is glucose pentapenta. Indicates acetate. * 2: AS is alkylsulfate sodium having 12 carbon atoms in the alkyl group,
LAS is a straight-chain sodium alkylbenzenesulfonate having an alkyl group having 12 to 13 carbon atoms, and ES is a sodium alkenyl ether sulfate having an alkenyl group having 12 carbon atoms. * 3: PEG6000 is polyethylene glycol with a molecular weight of 6000,
PPG1000 represents polypropylene glycol having a molecular weight of 1000.

As shown in Tables 1 to 3, the peracid production rate of Comparative Example 1 was 30%, which was significantly lower than the peracid production rates of Examples 1 to 21. From this, the effect of adding an anionic surfactant is clear. In addition, Example 1
Comparison between Nos. 2 and 8 revealed that the storage stability of Examples 2 and 8 was high. From this, it is clear that the solid or powdered acid is effective in improving the storage stability.
Also, comparing Examples 2 and 14, the coated Example 14 has higher storage stability. From this, the effect of improving storage stability by coating is clear. Further, comparing Examples 1 to 14 with Examples 15 to 21, Example 1
The solubility of 5 to 21 was better. From this, it is clear that the solubility can be improved by supplying water or supplying the bleach activator and / or anionic surfactant in a water slurry.

[0100]

EFFECTS OF THE INVENTION According to the present invention, the dissolution rate is fast even under the washing conditions of low temperature and weak agitation, or under the conditions of bleaching under pickling, and the dissolution rate is high, PC or PB
Even when blended with it, it became possible to obtain a bleach activator granulated product having excellent storage stability.

Claims (14)

[Claims] 1. A method for producing a bleach activator granule, which comprises compacting a bleach activator in the presence of water and / or a water-soluble binder and an anionic surfactant. 2. A bleach activator granulation, characterized in that the bleach activator is compacted in the presence of water and / or a water-soluble binder, an anionic surfactant and a solid or powdery acid. Method of manufacturing things. 3. The method for producing a bleach activator granule according to claim 1, wherein the water content in the total amount charged is 10% by weight or less. 4. The method for producing a bleach activator granulated product according to claim 1, wherein at least one of the bleach activator and the anionic surfactant is a water slurry. 5. The bleaching activator granules according to claim 4, wherein the bleaching activator and the anionic surfactant are dried while being sprayed with an aqueous slurry and then compacted. Method. 6. The water concentration in the total amount charged is 10 to 80% by weight.
And having a drying step.
A method for producing a bleach activator granule according to 2, 4, or 5. 7. The method for producing a bleach activator granulated product according to claim 1, wherein the bleaching activator is granulated after compaction molding. 8. A mixture of a bleach activator powder and water and / or a water-soluble binder and an anionic surfactant.
Alternatively, a mixture of a bleach activator powder, water and / or a water-soluble binder, an anionic surfactant, and a solid or powdery acid is mechanically extruded through an opening screen having a pore size of 500 to 5000 μm to form an elongated shape. By forming an extrudate and crushing it, the weight average particle size is 200 to 5000.
The method for producing a bleaching activator granule according to claim 1, 2, 3 or 7, wherein a bleaching activator granule having a size of µm is obtained. 9. The bleaching activator granules are bleaching activator 10 to 10.
95% by weight, water 0.2-10% by weight and / or water-soluble binder 0.3-40% by weight, anionic surfactant 5-65% by weight,
And a solid or powdery acid of 0 to 40% by weight, the method for producing a bleach activator granule according to any one of claims 1 to 8. 10. A group of bleach activators consisting of tetraacetylethylenediamine, glucose pentaacetate, tetraacetylglycoluril, a compound represented by the following general formula (I), and a compound represented by the following general formula (II). The method for producing a bleach activator granule according to any one of claims 1 to 9, wherein the method is one or a mixture of two or more selected from the following. Embedded image [In the formula, R ¹ represents an optionally substituted linear or branched alkyl group or alkenyl group having 1 to 22 carbon atoms, 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 group or alkenyl group having 1 to 22 carbon atoms). Y: 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 the number of 0 or 1. L: represents a leaving group that reacts with hydrogen peroxide to form an organic peracid. ] [Chemical 3] [In the formula, R ^{3 represents a} linear or branched alkyl group or alkenyl group having 1 to 22 carbon atoms, a phenyl group, or an alkyl-substituted aryl group having 1 to 20 carbon atoms in total of the alkyl substituents. R ⁴ and R ^{5 are the} same or different and each represents an alkyl group having 1 to 3 carbon atoms. [Chemical 4] (R ⁷ represents H or an optionally substituted linear or branched alkyl group or alkenyl group having 1 to 22 carbon atoms),
They may be the same or different. Y ₁ and Y ₂ : an optionally substituted alkylene group having 1 to 12 carbon atoms, an oxyalkylene group or a polyoxyalkylene group having 1 to 20 additional moles, which may be the same or different. n and m: each represents a number of 0 or 1. R ⁶ : an optionally substituted alkylene group having 1 to 12 carbon atoms or a compound represented by the formula: Represents a group represented by (q and r are numbers from 0 to 2). L: represents a leaving group that reacts with hydrogen peroxide to form an organic peracid. Z: an inorganic or organic anionic group (provided that 11. The bleaching activator granules obtained by the method according to any one of claims 1 to 8 is heated or cooled after or while adding and mixing a water-soluble polymer substance, or Production of a bleach activator granulated product characterized by obtaining a granulated product surface-coated with a water-soluble polymeric substance by adding or mixing an aqueous solution containing a water-soluble polymeric substance, or by drying while adding and mixing. Method. 12. The water-soluble polymer substance is a polysaccharide which may have a sulfate 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 bleach activator granule according to claim 11, which is a mixture of two or more species. 13. Bleach activator 10-95% by weight, water 0.2-
10% by weight and / or 0.3-40% by weight of water-soluble binder,
Contains 5 to 65% by weight of anionic surfactant and 0 to 40% by weight of solid or powdery acid, and has a weight average particle size of 200 to 50.
Bleach activator granules that are 00 μm. 14. A bleach activator granulated product according to claim 13.
A bleach activator granule having a weight average particle diameter of 200 to 5000 μm, having a coating layer of 0.5 to 50 parts by weight of a water-soluble polymer on the surface of 100 parts by weight.