JPH06128597A - Production of high-bulk-density granular detergent - Google Patents

Abstract

(57) [Summary] [Constitution] A surfactant containing at least one anionic surfactant and having a surfactant concentration of 60% by weight or more, with the total amount of the mixture to be mixed and pulverized being 100% by weight. Thick agent paste: 35 to 70% by weight, and an alkali builder containing at least carbonic acid or hydrogen carbonate and potassium salt:
30-65% by weight and powdered to obtain a powdered product, and the total amount of the mixture to be mixed and kneaded is 100% by weight, and the powdered product obtained in the above step: 45-95 weight%
And 5% to 5% by weight of zeolite are mixed, kneaded and then pulverized to produce a high bulk density granular detergent. [Effect] A surfactant salt, which does not easily deteriorate, is used as a starting material, and most or all of the surfactant is compounded in a detergent by a non-spray drying method, without requiring extra steps such as cooling and aging. It is possible to obtain a high bulk density granular detergent having excellent free-flowing properties and containing a high concentration of a surfactant.

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 high bulk density granular detergent containing a surfactant in a high concentration and having a high free flowability.

[0002]

2. Description of the Related Art Conventional laundry detergents contain a bulking agent having a bulk density of 0.1% by adding an extender (usually Glauber's salt) that hardly contributes to the cleaning performance to the composition and spray-drying it.
It was produced as bead-shaped hollow particles of about 3 g / cc.

However, since such a detergent has a low specific gravity and a low concentration of an activator, it is costly to transport and requires a considerable space for storage and display. It was difficult to weigh. Therefore, recently, a method for producing a high bulk density granular detergent which can be washed with a small amount of detergent has been proposed and put on the market. As a method for producing a high-bulk density granular detergent, the following techniques have been conventionally known, centering around the method for producing a laundry detergent, but all have drawbacks.

1) Japanese Unexamined Patent Publication (Kokai) No. 52-30962: A fatty acid having a melting point or higher is neutralized with water-containing powdery sodium carbonate to produce a powdery heavy detergent. <Disadvantage> Heating is required and the solubility of the obtained detergent is insufficient.

2) US Pat. No. 3,434,974: A method of neutralizing alkylbenzene sulfonic acid with sodium hydrogen carbonate, sodium tripolyphosphate and the like. <Disadvantage> Since the surfactant is treated from the acid state, deterioration of the acid with time becomes a problem, and sodium hydrogen carbonate needs to be used, and the product contains a relatively large amount of water.

3) JP-A-60-72999: Unneutralized sulfonated and / or sulfated compounds are neutralized and mixed with sodium carbonate and water, cooled to 40 ° C. or lower, and then pulverized together with powdery zeolite. Granulate. <Disadvantage> There is a problem of deterioration of an unneutralized product (acid), and excessive water is generated in the neutralization step. When pulverizing and granulating the mixture, an extra step such as lowering to 40 ° C. or lower is required.

4) Japanese Unexamined Patent Publication No. 2-86700: An aqueous surfactant paste and a dry detergency builder are mixed in a surfactant-builder ratio of 0.05: 1 to 1.5: 1 to prepare a dough. After forming, granulation is performed at a granulation temperature of −25 to 20 ° C. <Disadvantage> An extra step of cooling the dough to −25 to 20 ° C. is required for granulation.

5) Japanese Patent Laid-Open No. 61-69899: After spray-dried purified product is compacted, it is crushed and granulated in the presence of a surface modifier. <Disadvantages> Poor solubility in cold water and remarkable dust generation during production and products, resulting in poor commercial value. There is a step of spray-drying a concentrated slurry of surfactant, which is not energy saving.

[0009]

As described above, in the conventional method, if the concentration of the surfactant in the mixture is high, good granulation and pulverization cannot be generally performed, so that a cooling step and an aging step are required. Further, when the spray drying method is used, if a surfactant is blended in a high concentration in the system, not only 30 to 40% of water as water must be removed from the slurry, but also the obtained granular detergent It has a low bulk density.

Furthermore, when an acid as a precursor of a surfactant is used as a raw material and this is neutralized before use, it is necessary to take immediate measures such as immediate use and storage at low temperature because of the problem of deterioration. The present invention uses a surfactant salt, which does not easily deteriorate, as a starting material, and mixes most or all of the surfactant into a detergent by a non-spray drying method, without requiring extra steps such as cooling and aging. The present invention provides a method for producing a high bulk density granular detergent which is excellent in free flowing property and contains a surfactant in a high concentration.

[0011]

The method for producing a high bulk density granular detergent of the present invention is characterized by having the following first and second steps. (1) First step: a step of mixing the following components (a) and (b) into powder to obtain a powdered product, with the total amount of the mixture to be mixed and powdered being 100% by weight. (A) Surfactant concentrated paste containing at least one anionic surfactant and having a surfactant concentration of 60% by weight or more: 35 to 70% by weight. (B) Alkali builder containing at least carbonic acid or hydrogen carbonate and potassium salt: 30 to 65% by weight. (2) Second step: The total amount of the mixture to be mixed and kneaded is 1
The following components (A) and (B) are mixed, kneaded, and pulverized to 100% by weight. (A) Powdered product obtained in the first step: 45 to 95% by weight. (B) Zeolite: 55 to 5% by weight.

[0012]

DETAILED DESCRIPTION OF THE INVENTION

(1) First step: In the present invention, (a) a surfactant-rich paste is used as a main surfactant raw material component. (A) Surfactant concentrated paste contains at least an anionic surfactant, and may contain a nonionic surfactant and the like as necessary. By including a nonionic surfactant in the paste, the viscosity of the paste is reduced, and the paste can be highly concentrated and handled easily. Further, the nonionic surfactant may be simultaneously added during the powdering treatment by mixing with (b) the alkali builder. When a nonionic surfactant is added, it is added in the detergent composition in an amount of 0.5 to 20.
It is preferable to blend in a weight percentage, more preferably 3 to 1
There is 6% by weight.

As the anionic surfactant, for example, the following ones can be used, and sulfate ester type and sulfonate type are preferable. (1) A linear or branched alkylbenzene sulfonate having an alkyl group or an alkenyl group having an average carbon number of 10 to 18. (2) A higher alcohol sulfate ester salt having an alkyl group or an alkenyl group having an average carbon number of 10 to 18. (3) A higher alcohol ethoxylate sulfuric acid ester salt in which a saturated or unsaturated alcohol residue has an average carbon number of 10 to 18 and an average of 0.5 to 8 mol of ethylene oxide is added in one molecule. (4) An α-olefin sulfonate having an average carbon number of 10 to 18. (5) An α-sulfofatty acid alkyl ester salt in which a saturated or unsaturated fatty acid residue has an average carbon number of 10 to 18 and an alkyl group of the ester has 1 to 5 carbon atoms.

Typical salts are sodium salts and potassium salts. (A) Surfactant concentrated paste contains a total amount of surfactant of 60% by weight or more, preferably 60 to 95% by weight. If this amount is less than 60% by weight, the effect of adding an alkali builder containing carbonic acid or hydrogencarbonate and potassium salts in the powdering step is weakened, and the adhesion of the powdered product and the granular detergent is increased, making handling difficult. Becomes

Examples of the nonionic surfactant include the following. (1) Fatty acid polyoxyethylene alkyl ether represented by the following chemical formula 1

[0016]

[Chemical 1] (R₁CO: saturated or unsaturated fat having 8 to 18 carbon atoms
Acid residue n: shows the average number of moles of oxyethylene added, 8 to 30 R₂: Lower alkyl group having 1 to 5 carbon atoms)

(2) Carbon chain length of saturated or unsaturated alcohol 8 to 18 and average number of added moles of oxyethylene 8
~ 30 alcohol ethoxylates

As the alkali builder (b), a salt of carbonic acid or hydrogen carbonate and potassium, or a mixture of these with another alkali builder is used. The addition ratio of (b-1) carbonic acid or hydrogen carbonate / potassium salt and (b-2) another alkali builder is (b-1) / (b
-2) = 99/1 to 20/80 is preferable, and 60/40 to 35/75 is more preferable. If the ratio of carbonate or hydrogen carbonate and potassium salt in the alkali builder added to the surfactant thick paste is too low, the resulting powdered product and granular detergent have increased adhesiveness in the temperature range of the compounding conditions, Handling becomes difficult.

Examples of the salt of carbonic acid or hydrogen carbonate and potassium include potassium carbonate, potassium sodium carbonate, potassium hydrogen carbonate and the like. As the alkali builder other than carbonic acid or a salt of hydrogen carbonate and potassium, hydroxides such as sodium carbonate, sodium sesquicarbonate, sodium hydrogen carbonate, sodium hydroxide and potassium hydroxide are preferable.

In the present invention, first, both components (a) and (b) are mixed at the addition ratios shown in Table 1 below and powdered to obtain a surfactant powder. However, the total amount of the mixture is 10
It is a value when 0% by weight.

[0021]

[Table 1] Addition amount Preferred addition amount (a) Surfactant concentrated paste 35-70% by weight 45-67% by weight (b) Alkali builder 30-65% by weight 33-55% by weight

If the amount of the alkali builder with respect to the surfactant paste is too large, the amount of cleaning components in the finally obtained high bulk density granular detergent will decrease and the cleaning power will decrease. Also,
If the amount of alkali builder is too low, the adhesion of the powdered product increases and handling becomes difficult. When powdering with a surfactant paste and an alkali builder, by mixing the detergent formulation and the chelating builder as a cleaning aid in advance in the surfactant paste, or by adding them at the same time, during powdering and mixing It is possible to add a chelate builder to. As the chelate builder, zeolite having an ability to trap ions having a valence of 2 or more such as calcium, inorganic compound such as bentonite, sodium maleate-acrylic acid copolymer, organic compound such as β-alanine sodium diacetate Is mentioned.

The powdering method of the surfactant paste in the first step is carried out by using a strong shearing device such as a kneading machine and an alkali builder containing a salt of the surfactant paste and carbonic acid or hydrogen carbonate and potassium. Examples thereof include a method in which a chelate builder and a nonionic surfactant are mixed and kneaded as necessary, and then pulverized, and a method in which granulation is performed by stirring using a vertical or horizontal mixer. Specific examples of the apparatus used include a KRC kneader (Kurimoto Industry Co., Ltd.) and a Honda Continuous Kneader as a continuous apparatus in the case of a kneader, and a vertical kneader as a batch type apparatus. To be As a device for stirring and granulating using a mixer, there are a high speed mixer, a vertical mixer, and a turbulator (Hosokawa Micron Co., Ltd.).

(2) Second step: Next, (A) the surfactant powder obtained in the first step and (B) zeolite are mixed, or further other detergent components are mixed and kneaded. After that, it is pulverized to obtain the high bulk density granular detergent composition of the present invention. The powdered surfactant and the dry zeolite particles are mixed in the blending ratio shown in Table 2 below. The addition amount is a value when the total amount of the mixture is 100% by weight.

[0025]

[Table 2] Addition amount Preferred addition amount (A) Surfactant powder 45-95% by weight 65-93% by weight (B) Zeolite 55-5% by weight 35-7% by weight

If the amount of the powdered surfactant paste compounded is too low, the detergency is lowered, and conversely, if the amount is too high, the solubility of the high bulk density granular detergent composition obtained is deteriorated. As the zeolite, powdery dry particles may be used as they are, or a spray-dried product obtained by spray-drying from a slurry state together with other detergent compounding components may be used.

Other detergent components to be introduced when the powdered product containing the surfactant and the zeolite are mixed are a fluorescent agent and its aqueous solution, a pigment and its aqueous solution, sodium sulfite, sodium sulfate, anionic surface active agent. Examples of the agent and the solubility improver include a nonionic surfactant and the like. Each of these components may be added during mixing,
You may spray-dry with zeolite beforehand.

Mixing used to carry out the second step
The kneading device is not particularly limited, but a strong shearing device such as a kneader is preferable. Examples of continuous devices include KRC Kneader (Kurimoto Industry Co., Ltd.) and Honda Continuous Kneader, and examples of batch type devices include vertical kneaders.

By crushing the kneaded product, an average particle size of 3
About 0.00 to 600 μm, bulk density of 0.7 g / cc or more (J
A high bulk density granular detergent according to IS K3362 (6.2)) is obtained. In this crushing step, it is preferable to use a crushing aid such as an aluminosilicate, calcium carbonate or sodium carbonate having an average diameter of 10 μm or less.

Immediately after producing the high bulk density granular detergent, it is also possible to add an inorganic compound such as fine powder zeocate having a particle diameter of 10 μm or less as a fluidity improver.
Furthermore, it is also possible to powder blend the detergent particles of the high bulk density granular detergent particles of the present invention with a washing performance improving agent such as a chelate builder and an enzyme. As the chelate builder used here, powdered zeolite, sodium maleate-
Examples thereof include copolymers of acrylic acid and β-alanine sodium diacetate.

[0031]

EFFECTS OF THE INVENTION According to the present invention, (a) a concentrated surfactant paste, (b) carbonic acid or an alkali builder containing hydrogen carbonate and a potassium salt is mixed and powdered (A) a surfactant powder. After being made into a solidified product, the obtained (A) surfactant powdered product and (B) zeolite are mixed, kneaded and pulverized to mass produce a high bulk density granular detergent economically in a high yield. It becomes possible and is suitable as an industrial manufacturing method.

[0032]

【Example】

Example 1 Surfactant paste (surfactant concentration 75.2%) 56.3% by weight (composition: α-sulfofatty acid (C = 16 to 18) methyl ester sodium salt: 35.3% by weight higher alcohol (C = 11 to 13) ethoxy Rate Sulfate sodium salt (EOp = 3): 7.0 wt%) Potassium carbonate 23.0 wt% Sodium carbonate 20.7 wt% Total 100.0 wt%

The raw materials having the above composition were kneaded and mixed at 60 ° C. using a vertical kneader (manufactured by Dalton Co., Ltd.) and then molded by a pelletizer (manufactured by Fuji Paudal Co., Ltd.). For this kneaded product, finely powdered sodium carbonate (particle size 10
(μm) was added in an amount of 7.0% by weight and then pulverized with Fitzmill (manufactured by Hosokawa Micron Co., Ltd.) to obtain a particle size of 500-6.
A powder having a size of 00 μm was obtained.

Subsequently, the obtained powdered substance was mixed with zeolite and other detergent composition which were spray-dried.
The following composition was mixed and kneaded using a continuous kneader (manufactured by Kurimoto Industry Co., Ltd.). Surfactant powdered product 58.7% by weight Zeolite 26.9% by weight Fatty acid (C = 18) Polyoxyethylene 6.3% by weight Methyl ether (EOp = 15) α-sulfofatty acid (C = 14-16) Methyl ester Na salt 5.6% by weight Sodium sulfite 2.0 wt% Fluorescent agent 0.5 wt% 100.0 wt%

After adding 7.0% by weight of finely powdered sodium carbonate (particle size: 10 μm) as a grinding aid to the obtained kneaded product, it was crushed with a Fitzmill (manufactured by Hosokawa Micron Co., Ltd.) to give particles. Detergent particles having a diameter of 450 μm were obtained. Furthermore, 2.0% by weight of zeolite as a fluidity improving agent is coated on the detergent particles to obtain a bulk density of 0.85 g / cc.
A high bulk density granular detergent of The results are shown in Table 3. In the above composition, C represents the number of carbon atoms, and EOp represents the average number of added moles of oxyethylene.

Example 2 Surfactant paste (surfactant concentration 75.8%) 61.0 wt% (Composition: α-sulfofatty acid (C = 16-18) Methyl ester sodium salt: 40.2 wt% Fatty acid (C = 18) poly Oxyethylene methyl ether (EOp = 15): 6.0% by weight) Potassium carbonate 20.5% by weightSodium carbonate 18.5% by weight  Total 100.0% by weight

The raw material having the above composition was kneaded and mixed at 60 ° C. using a vertical kneader (manufactured by Dalton Co., Ltd.), and then molded by a pelletizer (manufactured by Fuji Paudal Co., Ltd.). For this kneaded product, finely powdered sodium carbonate (particle size 10
(μm) was added in an amount of 7.0% by weight and then pulverized with Fitzmill (manufactured by Hosokawa Micron Co., Ltd.) to obtain a particle size of 500-6.
A powder having a size of 00 μm was obtained.

Subsequently, the obtained powdered substance was mixed with zeolite and other detergent composition which were spray-dried.
The following composition was mixed and kneaded using a continuous kneader (manufactured by Kurimoto Industry Co., Ltd.). Surfactant powdered product 59.6% by weight Zeolite 30.4% by weight α-sulfofatty acid (C = 14-16) methyl ester Na salt 7.3% by weight Sodium sulfite 2.1% by weight Fluorescent agent 0.6% by weight 100.0% by weight

After adding 7.0% by weight of finely powdered sodium carbonate (particle size: 10 μm) as a grinding aid to the obtained kneaded product, it was ground with a Fitzmill (manufactured by Hosokawa Micron Co., Ltd.) to give particles. Detergent particles having a diameter of 470 μm were obtained. Furthermore, 2.0% by weight of zeolite as a fluidity improving agent is coated on the detergent particles to obtain a bulk density of 0.85 g / cc.
A high bulk density granular detergent of The results are shown in Table 3.

Example 3 Surfactant paste (surfactant concentration 75.8%) 49.0% by weight (composition: α-sulfofatty acid (C = 16-18) methyl ester sodium salt: 37.1% by weight) potassium carbonate 26.9% by weight carbonic acid Sodium 24.1% by weight Total 100.0% by weight

The raw materials having the above composition were kneaded by a vertical kneader (manufactured by Dalton Co., Ltd.) at 60 ° C., mixed, and then molded by a pelletizer (manufactured by Fuji Paudal Co., Ltd.). For this kneaded product, finely powdered sodium carbonate (particle size 10
(μm) was added in an amount of 7.0% by weight and then pulverized with Fitzmill (manufactured by Hosokawa Micron Co., Ltd.) to obtain a particle size of 500-6.
A powder having a size of 00 μm was obtained.

Subsequently, the obtained powdered substance was mixed with zeolite and other detergent composition which were spray-dried.
The following composition was mixed and kneaded using a continuous kneader (manufactured by Kurimoto Industry Co., Ltd.). Surfactant powder 48.9% by weight Zeolite 27.6% by weight Fatty acid (C = 18) Polyoxyethyl 6.8% by weight Methyl ether (EOp = 15) α-sulfofatty acid (C = 14-16) Methyl ester Na salt 13.5% by weight Sodium sulfite 2.7 wt% Fluorescent agent 0.5 wt% 100.0 wt%

After adding 7.0% by weight of finely powdered sodium carbonate (particle size: 10 μm) as a grinding aid to the obtained kneaded product, it was ground with a Fitzmill (manufactured by Hosokawa Micron Co., Ltd.) to give particles. Detergent particles having a diameter of 440 μm were obtained. Furthermore, 2.0% by weight of zeolite as a fluidity improving agent is coated on the detergent particles to obtain a bulk density of 0.85 g / cc.
A high bulk density granular detergent of The results are shown in Table 3.

Example 4 Surfactant paste (surfactant concentration 75.8%) 55.5 wt% (Composition: α-sulfofatty acid (C = 16-18) Methyl ester sodium salt: 34.6 wt% Fatty acid (C = 18) poly Oxyethylene methyl ether (EOp = 15): 7.5% by weight) Potassium carbonate 20.2% by weight Sodium carbonate 14.0% by weight Zeolite 10.3% by weight 100.0% by weight Total 100.0% by weight A turbulizer (manufactured by Hosokawa Micron Co., Ltd.) And granulate with stirring to obtain a particle size of 600-7
A powder having a size of 00 μm was obtained.

Subsequently, the obtained powdered substance was mixed with the spray-dried zeolite and other detergent compositions,
The following composition was mixed and kneaded using a continuous kneader (manufactured by Kurimoto Industry Co., Ltd.). Surfactant powder 82.4% by weight Zeolite 11.3% by weight α-sulfofatty acid (C = 14-16) methyl ester Na salt 3.2% by weight Sodium sulfite 2.6% by weight Fluorescent agent 0.5% by weight 100.0% by weight

After adding 7.0% by weight of finely powdered sodium carbonate (particle size: 10 μm) as a grinding aid to the obtained kneaded product, it was crushed with a Fitzmill (manufactured by Hosokawa Micron Co., Ltd.) to give particles. Detergent particles having a diameter of 450 μm were obtained. Further, 2.0% by weight of zeolite as a fluidity improving agent is coated on the detergent particles to obtain a bulk density of 0.82 g / cc.
A high bulk density granular detergent of The results are shown in Table 3.

Comparative Example 1 Surfactant slurry (surfactant concentration 75.8%) 66.4 wt% (Composition: α-sulfofatty acid (C = 16-18) Methyl ester sodium salt: 40.2 wt% Fatty acid (C = 18) poly Oxyethylene methyl ether (EOp = 15): 10.1% by weight) Sodium carbonate 33.6% by weight Total 100.0% by weight

The raw material having the above composition was kneaded and mixed at 60 ° C. using a vertical kneader (manufactured by Dalton Co., Ltd.), and then molded by a pelletizer (manufactured by Fuji Paudal Co., Ltd.). For this kneaded product, finely powdered sodium carbonate (particle size 10
(μm) was added in an amount of 7.0% by weight, and then pulverized with Fitzmill (manufactured by Hosokawa Micron Co., Ltd.). The obtained powder particles had a large adhesiveness, and they were used in a continuous kneader (manufactured by Kurimoto Industry Co., Ltd.) with the following composition together with the spray-dried zeolite and other detergent compositions. Mixing and kneading were performed. Surfactant powder 57.5% by weight Zeolite 32.2% by weight α-sulfofatty acid methyl ester sodium salt 7.8% by weight Sodium sulfite 2.0% by weight Fluorescent agent 0.5% by weight 100.0% by weight

After adding 7.0% by weight of finely powdered sodium carbonate (particle size: 10 μm) as a grinding aid to the obtained kneaded product, it was ground with a Fitzmill (manufactured by Hosokawa Micron Co., Ltd.). However, it was difficult to obtain powder particles because the adhesion to the blade and screen of the crusher was remarkable.

[0050]

[Table 3] Example ratio Comparative example 1 2 3 4 1 Detergent composition (wt%): α-SF * ¹ 29.0 32.3 23.9 38.8 31.7 AES * ² 4.0 − − − − Nonion * ³ − 4.1 − 6.9 6.5 Carbonic acid K 13.5 12.2 13.2 16.6 -Na carbonate 12.2 11.0 11.8 11.5 19.3 Zeolite 26.9 30.4 27.6 19.8 32.2 Other components 14.4 10.0 23.5 14.9 10.3 Properties: Average particle size 450 470 440 480-* ⁴ Bulk density (g / cc) 0.85 0.85 0.85 0.82 − * ⁴ Manufacturability Good Good Good Good Good Bad * ⁵ Angle of repose 45 45 40 40-* ⁴ * 1) α-SF: α-sulfo fatty acid methyl ester sodium salt * 2) AES: higher alcohol ethoxylate sulfate sodium salt * 3) Nonion: fatty acid polyoxyethylene alkyl ether * 4 ) Cannot be measured * 5) Large amount of blade and screen adhered

 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Kotaro Matsui 1-3-7 Main Office, Sumida-ku, Tokyo Lion Corporation

Claims (1)

[Claims] 1. The total amount of the mixture to be mixed and powdered is 100.
% By weight: (a) Surfactant concentrated paste containing at least one anionic surfactant and having a surfactant concentration of 60% by weight or more: 35 to 70% by weight, and (b) at least carbonic acid or carbonic acid. Alkali builder containing salt of hydrogen and potassium: 30 to 65% by weight is mixed and powdered to obtain a powdered product, and then the total amount of the mixture to be mixed and kneaded is 100% by weight, (A) Powdered material obtained in the above step: 45 to 95% by weight and (B) zeolite: 55 to 5% by weight are mixed, kneaded, and then pulverized, which is a method for producing a high bulk density granular detergent. .