JPH0680160B2 - 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 such as ease of carrying 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 in, for example, JP-A-51-67302.

In Japanese Patent Application Laid-Open No. 51-67302, spray drying is carried out by a granulating apparatus called Marmelizer under the trade name, which includes a substantially horizontal and rotatable rough surface table located inside and at the bottom of a substantially vertical smooth wall surface. Although a manufacturing method for densifying a powder detergent is disclosed and is a technology that pioneers the present invention, no consideration is given to the fluidity of the powder, and therefore the fluidity of the product is the original powder. It is worse than detergents and less convenient for consumers.

[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.
The fine powder obtained by subjecting the entire spray-dried product of the detergent containing the seed builder to pulverization, or the fine powder generated from the spray-drying facility and recovered from the dust-collecting facility, is placed horizontally in a horizontal mixing tank. With a mixer with a different stirring shaft and a mixer with a stirring blade attached to this shaft to mix powders or a mixer with a chopper for crushing or dispersing in this tank,
The apparent specific gravity is 0.62 to 1.1 by performing stirring granulation treatment in the presence of a surface modifier and a binder having an average diameter of 0.5 to 35 parts by weight with respect to 100 parts by weight of the spray-dried product and having an average diameter of 10 μm or less.
It is characterized by producing a powder detergent having a high density of 2 g / cm ³ and excellent fluidity. Here, the fine powder has an average particle size of
It means particles of 125 μm or less.

As the surface modifier, fine powder having an average diameter of 10 μm or less is used. Specifically, aluminosilicate is desirable because it functions as a calcium ion scavenger during washing. As the surface modifier, in addition to aluminosilicate, an inorganic fine powder selected from diacid silicon, bentonite, talc, and cry can be used. Also, metallic soap can be used in the same manner.

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 0.62 to 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 200 to 800 μm. Because 200μm
Generation of dust is seen at an average particle size of less than 800
This is because if it exceeds μm, the solubility tends to deteriorate.

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

1) Linear or branched alkylbenzene sulfonate having an alkyl group having an average carbon number of 10 to 16 2) A linear or branched alkyl or alkenyl group having an average carbon number of 10 to 20 and having one molecule 0.5 to 8 mol of ethylene oxide or propylene oxide or butylene oxide or ethylene oxide on average
Propylene oxide = 0.1 / 9.9 to 9.9 / 0.1 ratio or ethylene oxide / butylene oxide = 0.1 / 9.9
To 9.9 / 0.1 added alkyl or alkenyl ether sulfate 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 Olefin sulfonate having 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 number It has 10 to 20 alkyl groups or alkenyl groups and has an average of 0.5 to 8 moles in one molecule of ethylene oxide, propylene oxide, butylene oxide, or ethylene oxide / propylene oxide = 0.1 / 9.9 to 9.9 / 0.1 or ethylene. Oxide / butylene oxide = alkyl or alkenyl ether carboxylate added at a ratio of 0.1 / 9.9 to 9.9 / 0.1 8 ) Α-sulfo fatty acid salt or ester represented by the following formula (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 type surfactant 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. ) (R ₁ ′, R ₂ ′ and X are as described above. N is an integer of 1 to 5.) (R ₁ ′ is as described above. M is an integer of 1 to 8.) (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.) (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.) (R ₃ ′, R ₅ and X are as described above.) 10) Polyoxyethylene alkyl or alkenyl ether having an alkyl 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 mol. Ether 14) having an alkyl or 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 side 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 consisting of fatty acid having an average carbon number of 10 to 20 and sucrose 17) Fatty acid glycerin monoester consisting 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) Represented by the following general formula Betaine-type amphoteric activator (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.) (Here, R ₂₁ and R ₂₃ are as described above. N ₂ represents an integer of 1 to 20.) (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 surfactants 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. ) (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. ) (Here, R ₁₁ and R ₁₄ are as described above, and n ₁ is an integer of ₁ to 20.) 21) Phosphate ester activator (R 'is an alkyl or alkenyl group having 8 to 24 carbon atoms, n' + m '= 3, n' = 1 to 2) (R 'is n ″ + m ″ = 3, n ″ = 1 to 3 as described above. (R ', n ", m" are as described above, M'is Na, K, Ca) 22) Cationic surfactant 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 ′ Represents halogen.) (Here, R ₁ ′, R ₂ ′, R ₃ ′ and X ′ are as described above.) (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.

Of alkaline salts such as sodium carbonate, sodium sesquicarbonate, sodium silicate, neutral salts such as mirabilite, orthophosphate, pyrophosphate, tripolyphosphate, metaphosphate, hexametaphosphate, phytic acid and other phosphate salts. The following aluminosilicates may also be included.

Crystalline aluminosilicates x represented by the No.1-order equation '(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, 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) Phosphonocarboxylic acid salts such as 2-phosphonobutane-1,2-dicarboxylic acid, 1-phosphonobutane-2,3,4-tricarboxylic acid and α-methylphosphonosuccinic acid.

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

4) Aminopolyacetates such as nitrilotriacetate, ethylenediaminetetraacetate and diethylenetriaminepentaacetate.

5) Polyacrylic acid, polyaconitic acid, polyitaconic acid, polycitraconic acid, polyfumaric acid, polymaleic acid, polymethaconic acid, poly-α-hydroxyacrylic acid, polyvinylphosphonic acid, sulfonated polymaleic acid, maleic anhydride-diisobutylene copolymer Polymers, maleic anhydride-styrene copolymers, maleic anhydride-methyl vinyl ether copolymers, maleic anhydride-ethylene copolymers, maleic anhydride-ethylene crosslink copolymers, maleic anhydride-vinyl acetate copolymers 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, itaconic acid , Ethylene copolymer, itaconic acid-aconitic acid copolymer, 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-2,3,4-tricarboxylic acid-itaconic acid-acrylic acid copolymer, quaternary ammonium group-containing polyester polyaldehyde carboxylic acid 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,
Polymer electrolytes such as starch phosphate, dicarboxy starch, dicarboxymethyl starch, carboxymethyl cellulose, and succinate.

6) polyethylene glycol, polyvinyl alcohol,
Non-dissociated polymers such as polyvinylpyrrolidone and cold water soluble urethane 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, sucrose, lactose, raffinose and other carboxymethylated products, pentaerythritol carboxymethylated products, gluconic acid carboxymethylated products, 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-tricarboxylic acid, butane-1,4-dicarboxylic acid, oxalic acid, sulfosuccinic acid acid,
Decane-1,10-dicarboxylic acid, sulfotricarballylic acid, sulfoitaconic acid, malic acid, oxydisuccinic acid,
Organic acid salts such as gluconic acid, CMOS and Builder M.

(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 sulfate hydrogen peroxide adduct, etc.

(4) Enzyme (which is an enzyme that performs its original enzymatic action during the washing process) When classified according to the reactivity of the enzyme, 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 used: (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 contained 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 polyacrylic acid soda, 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 step in the method of the present invention will be described.
The entire amount of spray-dried detergent particles is subjected to grinding to obtain a fine powder. For the crushing, a type of shearing by a knife cutter rotating at high speed is suitable, or a crushing method by shearing and compression by a kneader 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, a horizontal mixing tank has a horizontal stirring shaft and a stirring blade is attached to this shaft to mix powder, or a mixer having a crushing or dispersing chopper in this tank. Then, the mixture is granulated while adding the surface modifier and the binder. 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 these additions, it is preferable to add a surface modifier as the last additive in order to further improve the fluidity of the detergent so that the surface of the detergent particles is covered with the surface modifier. 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, any of a Ledige mixer (Ldige Co.), a Spartan Luzer (Fuji Paudal Co., Ltd.) and a Pug mixer (Fuji Paudal Co., Ltd.) 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 silicon 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, 2.5 parts by weight of water, and 4 parts by weight of aluminosilicate fine powder having an average particle size of 2.7 μm were put in a Ledige mixer (Ldige), stirred and granulated, and then sieved with a 16 mesh screen. The coarse particles were removed.

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 instead 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.

Example 4 In Example 1, out of 4 parts by weight of the aluminosilicate fine powder used at the time of stirring and granulating, 1 part by weight was put into a Lodige mixer at the start of stirring and granulating, and the remaining 3 parts by weight was stirred and manufactured. One minute before the grain was finished, it was placed in the Loedige mixer.

Comparative Example 1 In Example 1, the procedure was carried out without using a surface modifier when granulating with stirring.

Comparative Example 2 In Example 1, the amount of the aluminosilicate added at the time of stirring and granulating was changed to 40 parts by weight.

Claims (5)

[Claims] 1. A spray-dried product of a detergent containing at least one surfactant and at least one builder, the whole amount of which has been subjected to pulverization, and then a horizontal mixing tank having a horizontal stirring shaft, Using a mixer of a type in which a stirring blade is attached to this shaft to mix powders, the presence of a binder and 0.5 to 35 parts by weight of a surface modifier having an average diameter of 10 μm or less with respect to 100 parts by weight of a spray-dried product is confirmed. A method for producing a high-density granular detergent with improved fluidity, which comprises subjecting the mixture to stirring granulation treatment to obtain high-density detergent particles having an apparent specific gravity of 0.62 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 powders or granular inorganic raw materials or (and) organic raw materials other than the spray-dried product are added and the granulation treatment is carried out at the same time. The manufacturing method described.