JPS621800A - Production of high density detergent composition - 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 a method for producing a high bulk density granular detergent composition by crushing and granulating detergent solids.Currently, granular detergents are mainly produced by spraying. Manufactured by drying method. In the spray drying method, detergent components such as surfactants and builders are mixed with added water to form a slurry with a moisture content of 35 to 50 υt%, and then this slurry is heated and sprayed into the heating space of a spray drying tower. Moisture 5-10wt%, bulk density 0.
The bead-like hollow particles are about 3 g/cc.

Although this method yields hollow granular detergent with excellent solubility, it has the problem of consuming a large amount of thermal energy because it is necessary to remove 30 to 40% of water by drying. The manufacturing equipment was large-scale, and a large capital investment was also required. Furthermore, there are restrictions on the production of detergents with a high content of surfactants, or on the use of heat-vulnerable substances such as nonionic surfactants that volatilize or decompose with heat, and also generate dust due to fine powder. However, it has the disadvantages that it is difficult to obtain a completely dust-free product.

As a method for producing granular detergents that does not involve spray drying, methods such as those disclosed in Japanese Patent Publication No. 7586/1986, Japanese Patent Publication No. 74703/1983, and Japanese Patent Publication No. 49535/1983 disclose methods for producing granular detergents using substances that have water of crystallization in advance as a raw material. There is a method of using a substance that is easily melted by heating, applying a thermal operation to release crystal water or melting the molten product, and using this as a binder, several to several dozen particles are agglomerated and granulated.

However, these methods have disadvantages such as the resulting granular detergent having a wide particle size distribution and poor solubility in water, and are not practically satisfactory.

The present inventors produced a high bulk density detergent by first kneading and mixing a detergent composition, disintegrating the kneaded product, and then coating it with water-insoluble fine powder with an average primary particle size of 10 μm or less. (Japanese Unexamined Patent Publication No. 60-96698), Shikashi and others have found that although the detergent obtained by this method has excellent powder properties, its solubility in water and detergency are still insufficient. There were even more improvements to be made.

It is known that polyacetal carboxylate has excellent calcium chelating ability and exhibits excellent detergency when incorporated into detergent compositions. However, polyacetal carboxylate has poor thermal stability and
Since it decomposes at about 210°C, the conventional production method using spray drying causes thermal deterioration such as burnt, and a sufficient addition effect cannot be achieved.

The present invention provides a method for producing a high bulk density detergent composition that can incorporate an organic chelating agent with excellent chelating ability without thermal deterioration, has excellent solubility, and exhibits great detergency. It is.

The method for producing the high bulk density detergent composition of the present invention is based on the following general formula (1
) A detergent composition containing one or more organic chelating agents selected from polyacetal carboxylate, ethylenediaminetetraacetate, and nitrilotriacetate having a skeleton represented by the following is kneaded, mixed, and then crushed. .

It is characterized by being coated with water-insoluble fine powder having an average primary particle size of 10 μm or less.

10cHo+r+ (t) ■ 000M (M: Alkali metal.

n: 40-300) The present invention will be explained in more detail below.

As the organic chelating agent, polyacetal carboxylate having a skeleton represented by the general formula (I), ethylenediaminetetraacetate (EDTA), and nitrilotriacetate (NTA) may be used alone or in combination of two or more. Representative salts of ED'TA and NTA are sodium salt and potassium salt. Among these,
Particularly preferred is polyacetal carboxylate.

Polyacetal carboxylates having a skeleton represented by general formula (1') are disclosed in, for example, U.S. Patent No. 4, 144
', No. 226 and No. 4,146,495. This polymer is stable under alkaline conditions, and undergoes hydrolysis under neutral or acidic conditions, and the decomposed segments can be biodegraded by microorganisms, making it suitable for heavy detergents that require high biodegradability from an environmental perspective. Suitable as a builder. In addition, this polymer has high calcium scavenging ability and good dispersion power for solid particles such as clay and carbon black.
It is also a builder with excellent cleaning performance. Polyacetal carboxylate is unstable to heat, but since the production method of the present invention does not require high-temperature treatment, it can be efficiently incorporated into high bulk density detergent compositions while preventing thermal deterioration.

Among polyacetal carboxylates, those whose terminal groups are protected with R or R2 are preferable in order to stabilize against depolymerization in an alkaline region, as shown in the following general formula (n).

(R engineering, R2 = terminal protecting group, M: alkali metal, n: IQ ~ 300) R1, R, are ether type oxygen, hydroxy group,
A saturated hydrocarbon group having oxygen in the form of a carboxy group is exemplified, and a specific example of this is c) (30-
, C, HsO-.

HO+CH, CH, O+,, HOCH2CH,+.

Moreover, as R2, -cH,, -CzHs.

+CH, CH2O+xH, -CH, C00M.

can be mentioned. Here, R represents hydrogen or a C1-3 alkyl group, and M represents an alkali metal or 1-4.

Of course, the stabilizing end groups are not limited to those mentioned above, and a mixture of a plurality of polyacetal carboxylates can also be used. ``The blending amount of the organic chelating agent is 1 to 20 wt%, preferably 3 to 15%+1%. The organic chelating agent has an average particle size of 50 to 1000 μm, preferably 50 to 200 μm.
It is blended into detergent compositions as a powder.

If the particle size is too large, the solubility will be poor, and if the particle size is too small, the powder will be difficult to handle.

In the detergent composition of the present invention, conventional detergent ingredients can be used as appropriate, such as anionic surfactants such as alkylbenzene sulfonates, alkyl sulfonates, α-olefin sulfonates, alkyl sulfates, and fatty acid soaps. agents, alkyl ethoxylates, alkylphenyl ethoxylates, nonionic surfactants such as alkylamides, amphoteric surfactants such as alkyl betaines, silicates,
Examples include alkali builders such as carbonates, bicarbonates, borates, percarbonates, and condensed polyphosphates, A-type zeolites, fluorescent agents, polyethylene glycols, carboxymethyl cellulose, and enzymes.

The organic chelating agent is intimately kneaded and mixed with other detergent components using a kneader or the like.

From the viewpoint of making the kneaded product easier to handle and improving its properties as a crushed raw material in the subsequent process, during kneading, the moisture content of the obtained kneaded product is 5 to 15% by weight.
It is better to adjust the moisture content and mix each component so that the moisture content is too low, and it is easy to turn into powder and generate dust during crushing. On the other hand, if it is too high, it will cause significant adhesion to the inside of the crusher. , continuous operation becomes difficult because it melts in the crusher. Note that the water content here includes water of crystallization of zeolite and the like.

Next, the detergent raw material densified product is uniformly kneaded.

It is crushed by a crusher and granulated. During crushing, the temperature of the crushed material increases due to frictional heat, so cold air, e.g.
It is preferable to introduce cold air of 0° C. or lower into the crusher for treatment, and it is desirable to introduce 100 or more cold air per 1 liter of crushed material.

For crushing, will a crusher be used that has a classification function such as screen classification or wind classification?

Alternatively, it is preferable to classify the crushed material using a sieve or the like and recycle unintended particles to form granules with a narrow particle size distribution.
It is granulated into μ■. The crusher has, for example, a multi-stage rotary crushing blade.

A device is used in which the crushed material is discharged through a 360° open screen, and the upper limit particle size can be set as desired by adjusting the opening of the screen. By shortening the time, over-grinding can be prevented and a sharp particle size distribution with a significantly reduced amount of fine powder can be obtained. A specific example of such a crusher is:
Speed mill ND-30 type (Okada Seiko M>) is an example.Of course, the crusher is not limited to this, and any suitable crusher can be used, but it is preferable to use one that can introduce cold air into the crushing chamber. During crushing, a crushing aid such as powdered sodium carbonate may also be added.

The granulated product obtained by crushing is then coated with water-insoluble fine powder to undergo surface modification. Note that the water-insoluble fine powder of the present invention also includes poorly water-soluble fine powder.

As water-insoluble fine powder, average particle diameter of 10 μm or less,
Preferably, particles with a particle size of 4 microns or less are used; if the particle size is too large, coating will not be uniform, and as a result, fluidity and storage stability will not be improved.

The coating equipment is transfer type and fluidized bed type.

Both types, such as a mixing type, are used, and water-insoluble fine powder adheres to the surface of the granulated product. The amount of water-insoluble fine powder added during coating is 0.5 to 5% by weight based on the granulated product.
is suitable. Specific examples of water-insoluble fine powder include calcium stearate dimagnesium stearate, aluminosilicates such as A-type zeolite, and calcium carbonate.

Examples include magnesium carbonate, magnesium silicate, silicon dioxide (white carbon), and titanium dioxide. By coating in this manner, adhesion 2 between detergent particles is suppressed and blocking due to storage is prevented. In addition, coating with fine powder improves the surface properties and improves fluidity, and excess water stays within the particles, improving solubility.

Furthermore, the granular detergent obtained as described above may be used as a product as it is by adding trace ingredients such as fragrances, or it may be used as a product as it is, or it may be used in a Marumerizer (Fuichi Paudal N) or in a cyclone-like device by being entrained in an air stream. It is also possible to size the particles by guiding them to a wall and making them come into contact with a wall surface to make the particles uniform in a substantially spherical shape, or to adjust the moisture content by drying with a little hot air.

According to the present invention, it is possible to extremely easily incorporate an organic chelating agent that is susceptible to thermal deterioration into a detergent composition.
The solubility can be greatly improved, and sufficient cleaning power can be achieved within the normal cleaning time.

Example Each component was kneaded using a kneader to obtain the composition shown in Table 1.

The obtained intimately mixed pellets (2'ca square) and A-type zaolite were quantitatively fed to a crusher (Okada Sei Nispeed Mill ND-30). At this time, 15° C. cold air was introduced together with the crushed material at a ratio of 151/kg of crushed material. The crusher rotated crushing blades with a diameter of 15 cm in four stages at 3000 rpm+, and the screen used was a punching metal with a 2 m-1 pore area ratio of 20%.

Next, 97 parts by weight of the obtained crushed product and 3 parts by weight of A-type zeolite having an average primary diameter of 3 μm were placed in a rolling drum (D = 30
cm, L = 60cm), 30r
pm and a residence time of 5 minutes to obtain a high bulk density granular detergent composition.

This detergent composition is arranged in 16# to 32# (bulk density 0.
9g/cc), the following dissolution test and detergency evaluation were conducted, and the results are shown in Table 1.

The abbreviations in Table 1 are as follows.

AO5-Na: Sodium α-olefin sulfonate having 14 to 18 carbon atoms LAS-Na(-K): Alkyl group having 10 to 1 carbon atoms
Linear alkylbenzenesulfonate sodium (potassium) of No. 4 PACI: Polyacetal carboxylate [n = average 86] PACII: Polyacetal carboxylate Ho+C
H2CH2o+-+CH-0 is also “←CH2CH,0→7
HCOON a ・ (n = average 84. Add 5Q of water and 250g of cloth, stir, and add the sample detergent all at once.The time of addition is time O, and about 20g of washing liquid is added every minute.
c), quickly filter it with suction, and measure the surfactant content of the filtrate. The time when this value reaches 95% of the theoretical value is defined as the dissolution time.

■Using a Hitachi washing machine (PS-5300, Aozora), wash artificial soiled cloth (cotton knitted) with water volume of 30n, bath ratio 30 times, sample usage amount of 25g, water temperature of 10℃ or Washed at 25°C for 10 minutes, then rinsed the items twice for 3 minutes each, dehydrated and dried, visually judged how well the stains had been removed using a 10-point scale, and evaluated the cleaning power of each sample. did.

(Margin below)

Claims (1)

[Claims] 1. A detergent composition containing one or more organic chelating agents selected from polyacetal carboxylate, ethylenediaminetetraacetate, and nitrilotriacetate having a skeleton represented by the following general formula (I). A method for producing a high bulk density detergent composition, which comprises kneading, mixing, crushing, and then coating with water-insoluble fine powder having an average primary particle size of 10 μm or less. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (M: Alkali metal, n: 10-300)