JPS62225599A - Production of granular detergent composition for mud contamination - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an industrial method for producing a granular detergent composition that exhibits excellent detergency against mud stains.

Conventional laundry detergent contains a large amount of alkaline agent and has a pH of 9.
Heavy detergents that clean with alkalinity of ~11 are the mainstream. These heavy detergents.

Although it has excellent cleaning power against sebum stains, etc.

The ability to remove mud stains was insufficient.

As a method for improving the cleaning ability against mud stains, the formulation of specific water-soluble ethoxylated cations (Japanese Unexamined Patent Publication No. 59-16
6599), a combination of cellulase and a bleaching agent (Japanese Patent Laid-Open No. 155299/1982), and a combination of sodium aluminosilicate and polyacetal carboxylate in a specific ratio (Japanese Patent Laid-open No. 147599/1989). There is. However, none of these methods has sufficient detergency against mud stains.

Currently, a lot of paint-on type detergents are used as specialized detergents for mud stains, but they require only spot cleaning, which is cumbersome.

Detergents containing a combination of acidic and alkaline substances are described in US Pat. No. 3,761,415 and German Patent No. 2.
, No. 437,173, and Japanese Patent Application Laid-open No. 13721/1983.

It is described in Publication No. 55-13722.

U.S. Patent No. 3,761,415 discloses that citrate ions are added prior to the alkaline agent in order to prevent the formation of water-insoluble salts (calcium carbonate, etc.) of the alkaline agent during cleaning in hard water. It is stated that Specific examples of this include adding an alkaline agent and a citrate separately, forming a tablet with an alkaline agent in the core and a citrate in the outer layer, and coating the alkaline agent with a water solubility retardant. It is stated that. However, this specification does not suggest any specific method for producing the above-mentioned tablet-type detergent.

German Patent No. 2,437,173 concerns a domestic cleaning process consisting of an acidic pre-cleaning, a main cleaning and a rinse, but this is complicated as it requires two stages of cleaning.

JP-A-55-13721 and JP-A-55-13722 describe a method in which an acid agent and an alkaline agent are made to exist separately, and the alkaline agent is protected with a coating or a sachet to delay its dissolution in water. ing. However, when sachets are used, the amount of detergent to be used per wash is determined, making it difficult for consumers to select a detergent that is appropriate for the amount of laundry and the degree of soiling. Further, when the acid agent and the coated alkali agent are mixed in powder form, classification occurs, and the initial objective of dissolving the alkali agent after the acid agent is dissolved may not be achieved.

Furthermore, the above-mentioned conventional techniques in which an acidic substance and an alkaline agent are combined are all intended to prevent calcium salts and magnesium salts (water-insoluble) of the alkaline agent from forming and adhering to cloth. is essentially a different technology, and there is no suggestion of mud and stain removal ability.

111 The present invention exhibits excellent detergency against mud stains, and furthermore,
The object of the present invention is to provide a method for industrially and simply producing a granular detergent composition that is easy to handle by consumers.

3 concentration 1 (7) t'il yield The method for producing the granular detergent composition for mud stains of the present invention includes the following (a) to ( c) It is characterized by passing through a process.

(a) A step of granulating a granulated product containing a sufficient amount of alkali builder and surfactant to make the liquid alkaline when the detergent particles are dissolved in water. The granulated particles have a bulk density of 0.
A process of increasing the bulk density by processing with a sizing machine until it becomes 7 g/cc or more, and making it into a detergent liquid.

(c) A step of coating the periphery of the high bulk density detergent liquid obtained in step (b) above with at least one polyhydric carboxylic acid and a surfactant that are solid at room temperature to form an acidic coating. .

The present invention will be explained in more detail below.

In step (a), granules containing at least an alkali builder and a surfactant are prepared. This granulation is performed by extrusion granulation, crush granulation, transfer granulation (agglomeration granulation), etc., and preferably produces granulated particles with a bulk density of 0.5 g/cc or more. It is desirable that the granulated particles have a uniform particle size, and if necessary, they are classified and the fine particles are recycled to the granulation process. The granulated particles mainly contain an alkali builder and a surfactant, and may also contain detergent components such as a chelating agent such as zeolite and a fluorescent whitening agent.

Examples of surfactants include 7-ion surfactants such as α-olefin sulfonates, linear alkylbenzene sulfonates, alkyl ether sulfates, alkyl sulfates, α-sulfo fatty acid ester salts, and polyoxyethylene alkyl phenyl ethers. , polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene alkylphenyl ether, polyoxyethylene polyoxypropylene alkyl ether, and other nonionic surfactants, which are commonly used as detergent components.

As the salt of the anionic surfactant, sodium salt and potassium salt are preferred. In order to effectively clean clothing stains, including mud stains, it is desirable that the granular detergent composition of the present invention contains 15% by weight or more of a surfactant. From the viewpoint of the blending amount of other detergent components and manufacturing, the amount of surfactant to be added to the granular detergent composition is
It is desirable that the amount is blended in weight%. As discussed below, at least a portion of this surfactant is incorporated into the acidic coating.

Alkali builders include carbonates, silicates (Na
zO/S iOz =2/1 to 1/3), and the salts include sodium salts and potassium salts. The alkali builder is added in an amount sufficient to make the liquid alkaline when the granular detergent composition is dissolved in water.
Preferably pH 9.0 or higher, more preferably P)19.
The amount is 0 to 10.5.

The preferred amount of alkali builder is 30 to 75% by weight based on the detergent composition.

The granulated detergent core particles are then reduced to 0.7 g in step (b).
The particles are sized until the bulk density is equal to or higher than /cc.

This sizing allows the detergent core components to become more compact.

The particles become spherical and become difficult to dissolve. Bulk density is 0.7g
If it is less than /cc, the dissolution rate of the detergent core becomes too fast,
It is not possible to exert sufficient cleaning power against mud and sludge rings.

This particle size regulation and high bulk density can be achieved using mechanical particle size machines such as Marumerizer (trade name, manufactured by Fuji Paudal),
This can be carried out using a wind-powered sieving machine described in the specification of No. 1092.

It is desirable that the detergent cores with a high bulk density obtained by sizing have a relatively large particle size, for example.

The average particle size is preferably about 0.5 to 3 μm. The larger the particles, the thicker the acidic coating can be set, and the more the detergent cores can be delayed in dissolution.

Next, the detergent core made to have a high bulk density in step (b) is coated with at least a surfactant and a polycarboxylic acid that is solid at room temperature to form an acidic coating.

As the polyhydric carboxylic acid, those having chelating ability are preferable, such as citric acid, ethylenediaminetetraacetic acid (ED
Examples include TA), nitrilotriacetic acid (NTA), tartaric acid, malonic acid, glutaric acid, and oxalic acid. This polyhydric carboxylic acid is 5 to 25% by weight based on the granular detergent composition.
It is preferably blended, more preferably 10 to 20% by weight.

If this amount is less than 5% by weight, it is difficult to uniformly coat the detergent cores, and the pH at the initial stage of washing cannot be made sufficiently acidic. On the other hand, if the amount exceeds 25% by weight, it will be difficult to make the pH sufficiently alkaline even in the latter half of washing when the detergent cores are dissolved. In any of the above cases, an effective mud removal effect cannot be achieved.

As the surfactant, those similar to those already explained in step (a) are preferred. The surfactant is desirably blended into the acidic coating in an amount of 5% by weight or more, more preferably 7% by weight or more, based on the entire granular detergent composition.

If a surfactant is not present during initial cleaning under an acidic atmosphere, an effective cleaning effect on the mud ring cannot be obtained.

As a method for coating the alkaline detergent core with an acidic coating, known techniques such as a transfer coating method using a one-dish type granulator or a drum-type granulator, a fluidized bed coating method, etc. may be used. At this time, a nonionic surfactant can be used as a binder and the polyhydric carboxylic acid powder can be coated.

Anionic surfactants can also be used in the form of fine powder. Further, water-insoluble fine powders such as zeolite and silicon dioxide can also be added.

Furthermore, prior to this coating, the detergent core can be coated with a poorly water-soluble, bright molecular film.

When the granular detergent composition of the present invention is poured into water, the polyhydric carboxylic acid and surfactant in the acidic coating are eluted in the initial stage of washing, and the mud ring is washed under acidic conditions. Then, after a time lag, the alkali builder and surfactant in the detergent core are dissolved, and the dirt is washed under alkaline conditions. At this time,
The pH is preferably 9 or higher, more preferably 9.0 to 10.5. In the manufacturing method of the present invention, the detergent cores are compacted into spherical shapes and have a high bulk density by sizing before being coated with the acidic coating. Dissolution can be delayed. Therefore, a sufficient time difference can be realized, and by combining acidic cleaning and alkaline cleaning, it is possible to exhibit excellent removal ability for mud and dirt.

INDUSTRIAL APPLICABILITY According to the present invention, a detergent composition having excellent dirt removal ability can be easily produced in the form of granules through simple operations, which is industrially useful.

Since the obtained detergent composition is a granular material that integrates the components necessary for cleaning, there is no need to separately add two components during washing, and there is no problem of classification of each component. It is extremely user-friendly for consumers, such as being able to adjust the amount of detergent depending on the amount of laundry.

In addition, since the obtained granular detergent has a high bulk density,
Storage space and transportation costs can also be significantly reduced compared to spray dryers.

JLK In the following examples, the mud and stain cleaning power was evaluated as follows.

'°Power'' Pour 5Q tap water into a 5Q small washing machine, add granular detergent composition for mud stains: 6.5g Mud stain cloth (5 cs + X 5 cm): 5 charged cloths (cutting a lined shirt) 150g of the sample was added at the same time and washed for 15 minutes.Afterwards, it was rinsed twice and air-dried.

The dirt cleaning power was calculated by the following formula by measuring the reflectance of the dirty cloth, and expressed as an index with the cleaning power of the control detergent (Comparative Example 1) set as 100.

The mud cloth was prepared as follows.

The dried Sankata raw mud is finely ground, dispersed in water, and coarse particles are cut with a 400# sieve to make a 15 g/Fl dispersion. A 5cm x 5c cotton plain woven cloth was dipped in this solution and air-dried to obtain a muddy cloth.

Example I AoS-Na” (spray-dried product) = 15 parts by weight Na2Co
: 30 parts by weight Na, 0-8iO, : 10 parts by weight Zeolite (type 4A): 15 parts by weight Water: 10 parts by weight Water 1)
C engineering. 1. Sodium α-olefin sulfonate The above ingredients are kneaded in a kneader, and the resulting solid detergent is pulverized in a pulverizer, with a particle size of 0.8 to 1.4 mm and a bulk density of 0.65 g.
/cc of granules were obtained. This granular material was applied for in 1986-14.
The particles were sized using the wind-powered sizing machine described in No. 1092, and the particle size was 0.
．． A detergent core having a bulk density of 8 to 1.4+++n+ and a bulk density of 0.83 g/cc was obtained.

To 80 parts by weight of this detergent core, 15 parts by weight of citric acid powder, alkylphenyl ethoxylate as a nonionic surfactant (C number of alkyl group = 12 to 14, average number of added moles of ethylene oxide (EO) = 9) 5 Comparative Example 1 In Example 1, the detergent core component and the acidic coating component were simultaneously kneaded in a kneader. Then, the obtained solid detergent is crushed to a particle size of 0.
The grain size is 8 to 1.4+ue, and then the bulk density is 0.
It was processed with a wind-type sizing machine until it became 82 g/cc to make a granular detergent.

Comparative Example 2 AoS-Na (spray-dried product) = 15 parts by weight Na2Go
,,: 30 parts by weight Na20-SiO,: 8.5 parts by weight Zeolite type 4A: 15 parts by weight The above components were agglomerated and granulated using a transfer drum using a 10% aqueous solution of sodium metasilicate as a binder, A small amount of excess water was dried and used as a detergent core. This detergent core has a particle size of 4
．． 8-1.4+nm, bulk density 0.55 g/cc,
Further, the composition was the same as in Example 1.

An acidic coating similar to that in Example 1 was formed on 80 parts by weight of this detergent core to obtain a granular detergent.

The mud and dirt cleaning power of the granular detergents of Example 1, Comparative Example 1, and Comparative Example 2 were compared, and the pH change of the washing liquid was also measured. The results are shown in Table-1.

Table 1 Example 2 The same procedure was used as in Example 1 except that the amount of AO8-Na in the detergent core and the amount of nonionic surfactant (APE) in the acidic coating were changed as shown in Table 2. Create granular detergent,
The ability to clean mud stains was evaluated.

Table-2 Example 3 LAS-K”: 10 parts by weight Na, COa: 30 parts by weight Nano-3in: 10 parts by weight Zeo 518815 parts by weight Including the inside: 10 weight.

x2) LAS acid and a 50% aqueous KOH solution were neutralized in a potassium kneader of a linear alkylbenzenesulfonate having an alkyl group having 10 to 14 carbon atoms, and other components were added to form the above composition, which was then kneaded. The obtained solid detergent was treated in the same manner as in Example 1 until the bulk density was 0.
Detergent cores of 85 g/cc and particle sizes of 1 to 21 IllI were produced.

Into this detergent core, various powdered organic acids shown in Table 3 are added.
5 parts by weight and nonionic surfactant (same as Example 1) 10
parts by weight were added and coated using a one-dish granulator to form an acidic coating to obtain a granular detergent composition. The mud and dirt cleaning power of these products was evaluated and shown in Table 3.

Table 3 Example 4 Granular detergents were prepared in the same manner as in Example 1 by varying the amount of citric acid in the acidic coating.

At this time, adjust the amount of sodium carbonate in the detergent core to the final p.
The H was changed to fall within the range of 9.0 to 1065, and balanced with Glauber's salt and water.

The influence of the amount of acidic substances was investigated as described above, and the results are shown in Table 4.

Table-4

Claims (1)

[Claims] 1. A granular detergent composition for mud stains, characterized in that the following steps (a) to (c) are carried out in producing detergent particles consisting of an alkaline detergent core and an acidic coating. manufacturing method. (a) A step of granulating a granule containing an alkali builder and a surfactant in an amount sufficient to make the liquid alkaline when the detergent particles are dissolved in water. (b) The granules granulated in step (a) above have a bulk density of 0.
．． A process of preparing detergent cores by processing with a sizing machine to increase bulk density until it becomes 7 g/cc or more. (c) A step of coating the periphery of the high bulk density detergent core obtained in step (b) with at least one polycarboxylic acid and a surfactant that are solid at room temperature to form an acidic coating. .