JPH07122079B2 - Process for making high density granular detergents with improved fluidity. - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a powder detergent having high density and excellent fluidity.

[Conventional technology and problems]

Conventionally, detergents used at home are required to have good productivity and be easy to handle and have good solubility when used by consumers. Therefore, most powder detergents produced by the spray drying method are used. there were. Here, the ease of handling means that the powder has a high free flowing property and is hard to be solidified, and that dust is not generated.

However, in recent years, there has been an increasing demand for high-density powder detergents because of the rationality from the viewpoint of resource saving and the convenience of being easily carried by consumers. High density means that the apparent specific gravity of the powder is 0.5 g / cm ³ or more. It is extremely difficult to obtain such a high-density powder detergent by the conventional spray drying method.

Generally, spray-dried detergent particles have an apparent specific gravity of 0.4 g / cm ^3.
Below, it is difficult to directly obtain high-density detergent particles having an average particle diameter of about 200 to 1000 μm.

On the other hand, the spray drying method has an advantage that any composition containing various raw materials such as anionic surfactant containing a large amount of water can be easily dried, except for a thermally unstable component. Therefore, by processing the spray dried detergent particles,
It has been desired to establish a manufacturing method for obtaining particles having high density and excellent fluidity.

An attempt to process spray-dried detergent particles to obtain a high-density powder detergent is disclosed, for example, in JP-A-51-67302.

In Japanese Patent Laid-Open No. 51-67302, the product name is Marumerizer,
A method of densifying spray-dried powder detergents by a granulator comprising a substantially horizontal, rotatable, rough surface table located inside and at the bottom of a substantially vertical smooth wall is disclosed, Although it is a pioneering technology of the present invention,
No consideration has been given to the fluidity of the powder, which makes the product less fluid than the original powdered detergent and less convenient for the consumer.

[Means for solving problems]

From the above technical background, as a result of research for producing a high-density powder detergent exhibiting good fluidity, the present invention described below was completed.

The present invention comprises at least one surfactant and at least one surfactant.
After the total amount of the spray-dried product of the detergent containing the seed builder was pulverized, a stirring shaft protruding from the bottom was installed inside the rigid mixing tank, and a stirring blade was attached to this shaft to mix the powder. Spray-dried product, depending on the type of mixing done
An apparent specific gravity of 0.7 is obtained by stirring granulation in the presence of 0.5 to 35 parts by weight of surface modifier and binder per 100 parts by weight.
It is characterized by obtaining high-density detergent particles of up to 1.2 g / cm ³ . Here, the fine powder means particles having an average particle diameter of 125 μm or less.

As the surface modifier, fine powder having an average diameter of 10 μm or less is preferably used. Specifically, aluminosilicate functions as a calcium ion scavenger during washing, which is desirable. As the surface modifier, in addition to aluminosilicate, an inorganic fine powder selected from silicon dioxide, bentonite, talc and clay can be used. Further, metal soap can be used as well.

The surface modifier achieves the purpose by using 0.5 to 35 parts by weight based on 100 parts by weight of the spray-dried detergent particles.
If the surface modifier is less than 0.5 parts by weight, it is difficult to obtain a powder exhibiting good fluidity, and if it exceeds 35 parts by weight,
If the fluidity is lowered and the amount of the binder is not increased unnecessarily, dust may be generated, which may impair the usability for consumers.

Furthermore, the apparent specific gravity of the high-density detergent particles is 0.7-1.2 g / cm ³
Is. This is because if the apparent specific gravity is larger than this, the solubility of the powder tends to be adversely affected. Moreover,
The average particle size is preferably 200 to 800 μm. This is because if the average particle size is less than 200 μm, dust is generated, and if it exceeds 800 μm, the solubility tends to deteriorate.

Surfactants that can be used in the present invention include the following.

1) A straight-chain or branched-chain alkylbenzene sulfonate having an alkyl group having an average carbon number of 10 to 16 2) A straight-chain or branched alkyl or alkenyl group having an average carbon number of 10 to 20 and one molecule 0.5 to 8 mol of ethylene oxide or propylene oxide or butylene oxide or ethylene oxide / propylene oxide = 0.1 / 9.9 to 9.9 / 0.1 or ethylene oxide / butylene oxide = 0.1 / 9.
Alkyl or alkenyl ether sulfate added at a ratio of 9 to 9.9 / 0.1 3) Alkyl or alkenyl sulfate having an alkyl group or alkenyl group having an average carbon number of 10 to 20 4) Average 10 to 20 carbon atoms in one molecule 5) Alkane sulfonate having an average of 10 to 20 carbon atoms in one molecule 6) Saturated or unsaturated fatty acid salt having an average of 10 to 24 carbon atoms in one molecule 7) Average carbon Having several 10 to 20 alkyl groups or alkenyl groups and having an average of 0.5 to 8 mol of ethylene oxide or propylene oxide or butylene oxide or ethylene oxide / propylene oxide = 0.1 / 9.9 to 9.9 / 0.1 per molecule Alkyl or alkenyl ether carboxylic acid added at a ratio of ethylene oxide / butylene oxide = 0.1 / 9.9 to 9.9 / 0.1 8) represented by the following formula α- sulfofatty acid salts or esters (In the formula, Y is an alkyl group having 1 to 3 carbon atoms or a counter ion, Z
Is a counterion. R represents an alkyl group or an alkenyl group having 10 to 20 carbon atoms. ) 9) Amino acid surfactant No. 1 represented by the following general formula (Wherein R ₁ ′ is an alkyl group or an alkenyl group having 8 to 24 carbon atoms, R ₂ ′ is hydrogen or an alkyl group having 1 to 2 carbon atoms,
R ₃ 'represents an amino acid residue, and X represents an alkali metal or alkaline earth metal ion. ) No.2 (R ₁ ′, R ₂ ′ and X are as described above. N is an integer of 1 to 5.) No. 3 (R ₁ ′ is as described above. M is an integer of 1 to 8.) No.4 (R ₁ ′, R ₃ ′ and X are as described above. R ₄ is hydrogen or an alkyl or hydroxyalkyl group having 1 to 2 carbon atoms.) No. 5 (R ₁ ′, R ₃ ′ and X are as described above. R ₅ is a β-hydroxyalkyl or β-hydroxyalkenyl group having 6 to 28 carbon atoms.) No. 6 (R ₃ ′, R ₅ and X are as described above.) 10) Polyoxyethylene alkyl or alkenyl ether having an alkyl group or alkenyl group having an average carbon number of 10 to 20 and having 1 to 20 mol of ethylene oxide added. 11) Polyoxyethylene alkylphenyl ether having an alkyl group having an average carbon number of 6 to 12 and having 1 to 20 mol of ethylene oxide added 12) Having an alkyl group or an alkenyl group having an average carbon number of 10 to 20 Polyoxypropylene alkyl or alkenyl ether to which propylene oxide is added in an amount of up to 20 moles 13) Polyoxybutylene alkyl or alkenyl having an alkyl or alkenyl group having an average carbon number of 10 to 20 and in which 1 to 20 moles of butylene oxide is added Ether 14) Having an alkyl group or an alkenyl group having an average carbon number of 10 to 20 and having a total of 1 to 30 mol of ethylene Nonionic activator with ethylene oxide and propylene oxide or ethylene oxide and butylene oxide added (ratio of ethylene oxide to propylene oxide or butylene oxide is 0.1 / 9.9 to 9.9 / 0.1) 15) Higher class represented by the following general formula Fatty acid alkanolamide or its alkylene oxide adduct (In the formula, R ₁₁ ′ is an alkyl group or an alkenyl group having 10 to 20 carbon atoms, R ₁₂ ′ is H or CH ₃ , n ₃ is an integer of 1 to 3, m ₃ is an integer of 0 to 3. 16) Sucrose fatty acid ester composed of fatty acid having an average carbon number of 10 to 20 and sucrose 17) Fatty acid glycerin monoester composed of fatty acid having an average carbon number of 10 to 20 and glycerin 18) Alkyl represented by the following general formula Amine oxide (In the formula, R ₁₃ ′ is an alkyl group or an alkenyl group having 10 to 20 carbon atoms, and R ₁₄ ′ and R ₁₅ ′ are alkyl groups having 1 to 3 carbon atoms.) 19) is represented by the following general formula. Betaine type amphoteric activator No.1 (Here, R ₂₁ is an alkyl or alkenyl having 8 to 24 carbon atoms or a β-hydroxyalkyl or β-hydroxyalkenyl group, R ₂₂ is an alkyl group having 1 to 4 carbon atoms, and R ₂₃ is an alkyl group having 1 to 6 carbon atoms or Indicates a hydroxyalkyl group.) No.2 (Here, R ₂₁ and R ₂₃ are as described above. N ₂ is an integer of 1 to 20.) No. 3 (Here, R ₂₁ and R ₂₃ are as described above. R ₂₄ has 2 to 5 carbon atoms.
Is a carboxyalkyl or hydroxyalkyl group. ) 20) Sulfonic acid type amphoteric surfactant No. 1 represented by the following general formula (Here, R ₁₁ is an alkyl or alkenyl group having 3 to 24 carbon atoms, R ₁₂ is an alkyl group having 1 to 4 carbon atoms, and R ₁₃ is 1 to 1 carbon atoms.
5 is an alkyl group, R ₁₄ is an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms. ) No.2 (Here, R ₁₁ and R ₁₄ are as described above. R ₁₅ and R ₁₆ have 8 carbon atoms.
-24 or 1-5 alkyl or alkenyl groups are shown. ) No.3 (Here, R ₁₁ and R ₁₄ are as described above, and n ₁ is an integer of ₁ to 20.) 21) Phosphate Ester Activator No. 1 Alkyl (or Alkenyl) Acid Phosphate Ester (R 'is an alkyl group or alkenyl group having 8 to 24 carbon atoms, n' + m '= 3, n' = 1 to 2) No.2 alkyl (or alkenyl) phosphate ester (R'is n "+ m" = 3, n "= 1 to 3 as described above) No.3 alkyl (or alkenyl) phosphate ester salt (R ', n ", m" are as described above, M'is Na, K, Ca) 22) Cationic surfactant No. 1 represented by the following general formula (Here, at least one of R ₁ ′, R ₂ ′, R ₃ ′ and R ₄ ′ is an alkyl or alkenyl group having 8 to 24 carbon atoms, and the other is an alkyl group having 1 to 5 carbon atoms. X ′ Indicates halogen.) No.2 (Here, R ₁ ′, R ₂ ′, R ₃ ′ and X ′ are as described above.) No. 3 (Here, R ₁ ′, R ₂ ′ and X ′ are as described above. R ₅ ′ is an alkylene group having 2 to 3 carbon atoms, and n ₄ is an integer of 1 to 20.) The content of the surfactant is 10-70% by weight, preferably 25-50
% By weight.

Inorganic builders that can be used in the present invention include the following.

Alkaline salts such as sodium carbonate, sodium sesquicarbonate and sodium silicate, neutral salts such as Glauber's salt, orthophosphate, pyrophosphate, tripolyphosphate, metaphosphate, hexametaphosphate and phytate Other than aluminosilicates can also be included.

No.1 Crystalline aluminosilicate represented by the following formula x ′ (M ₂ ′ O or M ″ O) · Al ₂ O ₃ · y ′ (SiO ₂ ) ·
w '(H ₂ O) (In the formula, M'is an alkali metal atom, M "is an alkaline earth metal atom exchangeable with calcium, and x', y ', w'represent the number of moles of each component. Specifically, 0.7 ≦ x ′ ≦ 1.5, 0.
8 ≦ y ′ ≦ 6, w ′ is an arbitrary integer. ) As the No. 2 detergent builder, those represented by the following general formula are particularly preferable.

Na ₂ O ・ Al ₂ O ₃・ nSiO ₂・ wH ₂ O (where n is a number from 1.8 to 3.0 and w is a number from 1 to 6) No.3 Amorphous aluminosilicate represented by the following formula x (M ₂ O) ・ Al ₂ O ₃・ y (SiO ₂ ) ・ w (H ₂ O) (In the formula, M represents a sodium and / or potassium atom, and x, y, w are within the following fine value ranges. It represents the number of moles of each component.

0.7 ≦ x ≦ 1.2 1.6 ≦ y ≦ 2.8 w is any positive number including 0) No.4 Amorphous aluminosilicate X (M ₂ O) ・ Al ₂ O ₃・ y (SiO ₂ )・ Z (P ₂ O ₅ ) ・ ω (H
₂ O) (In the formula, M represents Na or K, and X, Y, Z, and W represent the number of moles of each component within the range of the following numerical values.

0.20 ≤ X ≤ 1.10 0.20 ≤ Y ≤ 4.00 0.001 ≤ Z ≤ 0.80 W: any positive number including W) Further, in the present invention, the following additives can be used.

(1) Divalent metal ion scavenger 1) ethane-1,1-diphosphonic acid, ethane-1,2-triphosphonic acid, ethane-1-hydroxy-1,1-diphosphonic acid and its derivatives, ethanehydroxy-1, Phosphonates such as 1,2-triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid and methanehydroxyphosphonic acid.

2) 2-phosphonobutane-1,2-dicarboxylic acid, 1-
Phosphonocarboxylic acid salts such as phosphonobutane-2,3,4-tricarboxylic acid and α-methylphosphonosuccinic acid.

3) Amino acid salts such as aspartic acid and glutamic acid.

4) Nitrilotriacetate, ethylenediaminetetraacetate,
Aminopolyacetates such as diethylenetriaminepentaacetate.

5) Polyacrylic acid, polyaconitic acid, foliitaconic acid, polycitraconic acid, polyfumaric acid, polymaleic acid, polymethaconic acid, poly-α-hydroxyacrylic acid, polyvinylphosphonic acid, sulfonated polymaleic acid, maleic anhydride-diisobutylene copolymer Polymer, heavy water maleic acid-styrene copolymer, heavy water maleic acid-methyl vinyl ether copolymer, maleic anhydride-ethylene copolymer, maleic anhydride-ethylene crosslink copolymer, maleic anhydride-vinyl acetate copolymer Combined, maleic anhydride-acrylonitrile copolymer, maleic anhydride-acrylic acid ester copolymer, maleic anhydride-butadiene copolymer, maleic anhydride-isoprene copolymer, derived from maleic anhydride and carbon monoxide Poly-β-ketocarboxylic acid, itacone , Ethylene copolymer, itaconic acid - aconitic Santomo polymers, itaconic acid - maleic acid copolymer, itaconic acid - acrylic acid copolymer, malonic acid - methylene copolymer, metaconic acid - fumaric acid copolymer,
Ethylene glycol-ethylene terephthalate copolymer, vinylpyrrolidone-vinyl acetate copolymer, 1-butene 12,3,4-tricarboxylic acid-itaconic acid-acrylic acid copolymer, quaternary ammonium group-containing polyester polyaldehyde carboxylic acid , Cis-isomer of epoxysuccinic acid, poly [N, N-bis (carboxymethyl) acrylamide], poly (oxycarboxylic acid), starch succinic acid or maleic acid or terephthalic acid ester, starch phosphoric acid ester, dicarboxystarch , Dicarboxymethyl starch, carboxymethyl cellulose,
Polymer electrolyte such as succinate.

6) Non-dissociated polymers such as polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, and cold water-soluble urethanized polyvinyl alcohol.

7) Diglycolic acid, oxydisuccinic acid, carboxymethyloxysuccinic acid, cyclopentane-1,2,3,4-tetracarboxylic acid, tetrahydrofuran-1,2,3,4-tetracarboxylic acid, tetrahydrofuran-2,2, 5,5-Tetracarboxylic acid, citric acid, lactic acid, tartaric acid, saccharose, lactose, raffinose and other carboxymethyl compounds, pentaerythritol carboxymethyl compounds, glycolic acid carboxymethyl compounds, polyhydric alcohols or sugars and maleic anhydride Or a condensate with succinic anhydride, a condensate with an oxycarboxylic acid and maleic anhydride or succinic anhydride, a benzene polycarboxylic acid represented by mellitic acid, ethane-1,1,2,2-tetracarboxylic acid, Ethene-1,1,2,2-tetracarboxylic acid, butane-1,2,3,4-tetracarboxylic acid, propane-1,2,3-trica Boronic acid, butane-1,4-dicarboxylic acid, oxalic acid, sulfosuccinic acid, decane-1,10-dicarboxylic acid, sulfotricarballylic acid, sulfoitaconic acid, malic acid, oxydisuccinic acid, gluconic acid, CMOS, Builder M, etc. Organic acid salts.

(2) Anti-soil redeposition agent Further, one or more of the following compounds as an anti-soil redeposition agent can be contained in the composition in an amount of 0.1 to 5%. Polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, carboxymethyl cellulose, etc.

(3) Bleaching agent Sodium percarbonate, sodium perborate, sodium hydrogen peroxide adduct, etc.

(4) Enzymes (enzymes that perform the original enzymatic action during the washing process) When classified according to the reactivity of enzymes, hydrolases, hydrolases, oxidoreductases, desmolases, transferases and isomerases can be mentioned. Any of the above can be applied to the present invention. Particularly preferred are hydrolases, such as proteases, esterases,
Includes carbohydrases and nucleases.

Specific examples of proteases include pepsin, trypsin, chymotrypsin, collagenase, keratinase, elastase, sputillin, BPN, papain, promerin, carboxypeptidases A and B, aminopeptidase,
Aspar gyropeptidases A and B.

Specific examples of esterases include gastric lipases, pancreatic lipases, plant lipases, phospholipases, cholinesterases and phosphotases.

Carbohydrase includes cellulase, maltase, saccharase, amylase, pectinase, lysozyme, α-
Glycosidases and β-glycosidases.

(5) Bluing agent Various bluing agents can be added as needed. For example, the following structure is recommended: (Wherein D represents a blue to purple monoazo, disazo or anthraquinone dye residue, and X and Y may be substituted with a hydroxyl group, an amino group, a hydroxyl group, a sulfonic acid group, a carboxylic acid group or an alkoxy group. An aliphatic amino group, a halogen atom, a hydroxyl group, a sulfonic acid group, a carboxylic acid group, a lower alkyl group, or an aromatic amino group which may be substituted with a lower alkoxy group or a cycloaliphatic amino group.
R is a hydrogen atom or a lower alkyl group. However, the case where R represents a hydrogen atom and X and Y simultaneously represent a hydroxyl group or an alkanolamino group, and the case where either one of X and Y is a hydroxyl group and the other is an alkanolamino group is excluded. n represents an integer of 2 or more. ) (In the formula, D represents a blue to purple azo or anthraquinone dye residue, and X and Y represent the same or different alkanolamino residues or hydroxyl groups.) (6) Anti-caking agent Paratoluenesulfonate, Xylene sulfonate, acetate, sulfosuccinate, talc, finely divided silica, clay, calcium-silicate (eg, Johns Manvill Microcell), magnesium oxide and the like.

(7) Antioxidant tert-butyl hydroxytoluene, 4,4'-butylidene bis- (6-tert-butyl-3-methylphenol), 2,
2'-butylidene bis-(-tert-butyl-4-methylphenol), monostyrenated cresol, distyrenated cresol, monostyrenated phenol, distyrenated phenol, 1,1'-bis- (4-hydroxyphenyl) cyclohexane, etc. Antioxidant.

(8) Fluorescent dye 4,4′-bis- (2-sulfostyryl) -biphenyl salt, 4,4′-bis- (4-chloro-3-sulfostyryl) -biphenyl salt, 2- (styrylphenyl) Naphthothiazole derivative, 4,4'-bis (triazole-2-
Yl) stilbene derivative, bis (triazinylamino)
One or more of the stilbene disulfonic acid derivatives,
It can be contained in the composition in an amount of 0 to 1% by weight.

(9) Photoactivated bleaching agent One or two kinds of sulfonated aluminum phthalocyanine and sulfonated zinc phthalocyanine are used in the composition in an amount of 0 to 0.2.
It may be contained in a weight percentage.

(10) Fragrances Binders that can be used in the present invention include water-soluble polymer solutions of carboxymethyl cellulose, polyethylene glycol, polycarboxylic acid salts such as sodium polyacrylate, polyoxyethylene alkyl ether, fatty acid monoethanolamide, fatty acid diethanolamid. Examples thereof include nonionic substances such as sodium chloride, sodium silicate aqueous solution, and water.

In carrying out the present invention, spray-dried detergent particles can be obtained as follows. That is, a thermally unstable raw material,
For example, it consists of enzymes, bleach, and inorganic builders that do not need to be dried, such as sodium carbonate and sodium sulfate, and anionic surfactant solutions that need to be dried, aluminosilicate slurries, fluorescent dyes, pigments, etc. Spray dry the slurry. If the spray dried particles are very sticky,
Mixing sodium carbonate, sodium sulfate, sodium silicate, etc. into the detergent slurry is optional.

The apparent specific gravity and particle size of the spray-dried detergent particles do not matter. The water content is preferably 12% or less. If there is more water than that, the fluidity of the granulated particles will be adversely affected.

Next, the crushing process in the method of the present invention will be described.
The spray-dried detergent particles are ground to give a fine powder. For crushing, a type of shearing with a knife cutter rotating at a high speed is suitable, but a crushing method by shearing with a kneader and compression can also be applied. In the pulverizing step, it is effective to mix and use a part of the above-mentioned surface modifier to prevent adhesion to the pulverizer. In this step, other inorganic raw materials and / or organic raw materials other than the spray-dried product may be mixed.

The fine powder generated from the spray drying facility and recovered in the dust collecting facility may be used alone or in combination with the above fine powder obtained by crushing.

Subsequent to the above steps, while adding a surface modifier and a binder with a mixer of a type having a stirring shaft protruding from the bottom inside a rigid mixing tank and mixing a powder by attaching a stirring blade to this shaft. Mix and granulate. The surface modifier and the binder may be added at the same time, or either of them may be added first, or they may be added alternately. In this step, it is optional to mix other inorganic raw materials and / or organic raw materials of the detergent.

As an example of the mixer used in the present invention, either a high speed mixer (stirring granulator) or a Henschel mixer (high speed stirring granulator) can be used.

The detergent particles produced by the present invention can be easily distinguished from the detergent particles produced by other production methods by having the following two characteristics.

One of them is that the particle surface is covered with a surface modifier, which can be easily confirmed by observation with an electron microscope.

Another feature is that the mechanically disrupted spray dried particles comprise the detergent particles of the present invention. This is because when the detergent particles are dipped in ethyl alcohol, the detergent particles of the present invention are dispersed as fine powder, whereas the particles of the clothes detergent simply spray-dried are not dispersed in this way, so that the detergent particles are easily dispersed. I can confirm.

〔Example〕

Examples of the present invention will be shown below, but these examples do not limit the present invention.

Example 1 A detergent having the following composition was spray-dried.

Linear alkylbenzene sulfonate 35 parts by weight Alkyl sulfate ester salt 10 〃 Sodium carbonate 21.5 〃 Sodium silicate 7 〃 Sodium aluminosilicate 14 〃 Sodium sulfate 6 〃 Nonionic surfactant 3.5 〃 Moisture 3 〃 Average of obtained detergent particles The particle size was 430 μm, and the apparent specific gravity was 0.29 g / ml.

After mixing 3 parts by weight of aluminosilicate fine powder having an average particle size of 2.7 μm with 100 parts by weight of the detergent particles in a V blender, 24
Grinded with a flash mill (Fuji Paudal Co., Ltd.) equipped with a mesh screen to give an average particle size of 19
A powder having a particle size of 0 μm and an apparent specific gravity of 0.39 was obtained.

100 parts by weight of this powder, 2 parts by weight of water, and 4 parts by weight of aluminosilicate fine powder having an average particle size of 27 μm were put into a high speed mixer (manufactured by Fukae Kogyo Co., Ltd.) and stirred and granulated.
Coarse particles were removed with a 16-mesh sieve.

The apparent specific gravity, average particle size, and fluidity of the detergent thus obtained were measured and shown in Table 1 together with other examples and comparative examples.

Here, the fluidity of the powder, from the hopper for measuring the apparent specific gravity specified in JIS K 3362, the time required for 100 ml of powder to flow out is measured, and the shorter the time, the better the fluidity is determined to be. To do.

Example 2 In Example 1, 1 part by weight of silicon dioxide fine powder having a particle size of 20 mμ (0.02 μm) was used in place of the aluminosilicate fine powder used in the stirring granulation.

Example 3 In Example 1, 2 parts by weight of the same aluminosilicate and 2 parts by weight of talc fine powder having an average particle size of 1.5 μm were combined instead of the aluminosilicate fine powder used in the stirring granulation. Using.

Comparative Example 1 In Example 1, the procedure was carried out without using the surface modifier at the time of stirring granulation.

Comparative Example 2 In Example 1, 40 parts by weight of the aluminosilicate added at the time of stirring granulation was added to carry out stirring granulation.

Claims (6)

[Claims] 1. A stirring shaft projecting from the bottom into a rigid mixing tank after pulverizing the whole amount of a spray-dried product of a detergent containing at least one surfactant and at least one builder. And agitating granulation in the presence of 0.5 to 35 parts by weight of the surface-modifying agent and binder per 100 parts by weight of the spray-dried product by a mixer of a type in which a stirring blade is attached to this shaft to mix the powder. Apparent specific gravity is 0 after processing.
A method for producing a high-density granular detergent with improved fluidity, which comprises obtaining high-density detergent particles of 7 to 1.2 g / cm ³ . 2. The method according to claim 1, wherein the surface modifier is an aluminosilicate. 3. The surface modifier is silicon dioxide, bentonite,
The method according to claim 1, which is an inorganic fine powder selected from talc and clay. 4. The method according to claim 1, wherein the surface modifier is a metal soap. 5. The method according to any one of claims 1 to 4, wherein the surface modifier has an average diameter of 10 μm or less. 6. The method according to any one of claims 1 to 5, wherein a powder or granular inorganic raw material or / and an organic raw material other than the spray-dried product is added and the granulation treatment is carried out at the same time. The method described.