JPH0639599B2 - Method for producing high bulk density detergent composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a method for producing a high bulk density detergent composition containing a sulfonated salt of a saturated fatty acid ester as an active ingredient.

2. Description of the Related Art Sulfonated salts of saturated fatty acid esters are surfactants having excellent detergency and hard water resistance, and are attracting attention as active ingredients of phosphorus-free detergents.

However, sulfonated salts of saturated fatty acid esters are easily hydrolyzed by heat, and if an attempt is made to make a granular detergent by a spray drying method that has been generally used in the past, the ester will be hydrolyzed during spray drying, resulting in washing. There was a problem that it changed into a disodium salt of sulfo fatty acid having low strength.

Further, the sulfonated salt of an ester of saturated fatty acid has a problem of poor rinsing property since it causes more foaming at a lower concentration than other surfactants such as an alkylbenzene sulfonate. As a method of improving this rinsability, the present applicant has previously proposed to blend a sulfonated salt of a saturated fatty acid ester with a sulfonated salt of an unsaturated fatty acid ester. However, the sulfonated salt of unsaturated fatty acid ester is unstable to heat, and there is a problem that the physical properties of powder are deteriorated when this compound is granulated by spray drying. Thus, in a detergent system incorporating both saturated and unsaturated sulfonated salts of fatty acid esters,
It is necessary to further suppress decomposition in the manufacturing process,
In addition, the storage stability is not sufficient, and satisfactory characteristics have not been obtained.

OBJECT OF THE INVENTION The present invention provides a method for producing a high bulk density granulated detergent which prevents decomposition of a sulfonated product of a saturated and unsaturated fatty acid ester due to heat during the production of a detergent and which is excellent in powder physical properties. Is.

The high-bulk density detergent composition of the present invention comprises kneading, mixing and crushing a detergent composition containing a sulfonated salt of a saturated fatty acid ester and a sulfonated salt of an unsaturated fatty acid ester, followed by crushing, and then crushing. It is characterized by coating with a water-insoluble fine powder having an average primary particle size of 10 μm or less.

Hereinafter, the present invention will be described in more detail.

A typical sulfonated salt of a saturated fatty acid ester is a sulfonated salt of a lower alkyl ester of a saturated fatty acid having a fatty acid residue having 12 to 20 carbon atoms, and a lower alkyl group having 1 to 6 carbon atoms. The ones are suitable. Of these, fatty acid residues having 14 to 18 carbon atoms and lower alkyl groups having 1 to 2 carbon atoms are preferable. As the salt, an alkali metal salt, an alkaline earth metal salt, an ammonium salt,
Examples are organic base salts such as amine salts.

The sulfonated salt of a saturated fatty acid ester is suitably used in an amount of 5 to 30% by weight, preferably 10 to 25% by weight, in the resulting high bulk density detergent composition.

The sulfonated salt of unsaturated fatty acid ester is typically a sulfonated salt of a lower alkyl ester of an unsaturated fatty acid having a fatty acid residue having 16 to 22 carbon atoms, and the lower alkyl group has 1 carbon atom. Those of up to 6 are suitable. Of these, fatty acid residues having 16 to 18 carbon atoms and lower alkyl groups having 1 to 2 carbon atoms are preferable. Examples of salts include organic base salts such as alkali metal salts, alkaline earth metal salts, ammonium salts, and ami salts. The typical structural formula is as follows.

Alkenyl monosulfonate (R, R ': alkyl group or alkenyl group, M: salt) Thus, the salts of unsaturated fatty acid ester sulfonates also include sulfonates not containing double bonds such as hydroxymonosulfonate. Be done.

(b) The sulfonated salt of unsaturated fatty acid ester is (a) / (b) with respect to the sulfonated salt of saturated fatty acid ester.
It is suitable to mix it in the ratio of 10/1 to 1/2, preferably 3/1 to 1/1.

The sulfonated salt of a saturated fatty acid ester has a strong foaming property and has poor rinsability, but the rinsability can be improved by blending it with a sulfonated salt of an unsaturated fatty acid ester. The sulfonated salt of an unsaturated fatty acid ester is unstable to heat, and when granulated by a spray drying method which has been generally adopted conventionally, it is decomposed by heating and the powder physical properties deteriorate. On the other hand, according to the production method of the present invention, decomposition of the salt of the sulfonated product of unsaturated fatty acid ester is prevented without being exposed to high temperature in the production process, and as a result, deterioration of powder physical properties is suppressed. In addition, the effect of improving rinsability can be sufficiently exerted.

The sulfonated salt of saturated fatty acid ester and the sulfonated salt of unsaturated fatty acid ester are intimately kneaded and mixed with other detergent components in a kneader or the like. Other detergent components include, for example, anionic surfactants such as alkyl sulfates and alkylaryl sulfonates, amphoteric surfactants such as alkyl betaines, nonionic surfactants such as alkyl ethoxylates, and silicates. Carbonate,
Alkali builders such as hydrogencarbonate, percarbonate, borate, perborate, tripolyphosphate, pyrophosphate (sodium or potassium salt), sodium citrate, sodium ethylenediaminetetraacetate, zeolite, nitrilo Examples include chelate builders such as sodium triacetate and neutral builders such as sodium sulfate.

From the viewpoint of facilitating the handling of the kneaded product and improving the characteristics as a crushing raw material in the subsequent step, the kneaded product should have a water content of 5 to 15% by weight. It is preferable to adjust the water content and mix the components. If the water content is too small, it tends to be pulverized and dust is generated during crushing, while if it is too large, the adherence to the inside of the crusher becomes remarkable and it is melted inside the crusher, making continuous operation difficult. Here, the water content is an amount that also includes crystal water such as zeolite.

The detergent raw material compact that is uniformly kneaded with a kneader or the like is then crushed by a crusher and granulated. At the time of crushing, the temperature of the crushed material rises due to frictional heat, so it is preferable to introduce cold air, for example, cold air at 20 ° C or less, into the crusher for treatment, and it is desirable to introduce 10 or more cold air per 1 kg of crushed material. .

For crushing, use a crusher equipped with a classifying function such as screen classifier, wind classifier or the like, or classify the crushed product with a sieve and recycle the undesired particle size product to obtain a narrow range. It is desirable to granulate to a particle size distribution, for example, an average particle size of 300 to 2000 μm. As the crusher, for example, a crusher having a multistage rotary crushing blade and discharging the crushed material through a 360 ° release screen is used. It can be set, and by shortening the residence time of the crushed material in the crushing chamber, overcrushing can be prevented, and a sharp particle size distribution in which the amount of fine powder is extremely small can be obtained. A specific example of such a disintegrator is a speed mill ND-30 type (Okada Seiko Co., Ltd.).
Of course, the disintegrator is not limited to this, and any appropriate disintegrator can be used, but a disintegrator capable of introducing cold air into the disintegrator is desirable. Further, upon crushing, a crushing aid such as powdered sodium carbonate can be added.

The granulated product obtained by the crushing is then coated with a water-insoluble fine powder for surface modification. The water-insoluble fine powder of the present invention includes a poorly water-soluble fine powder.

As the water-insoluble fine powder, those having an average primary particle size of 10 μm or less, preferably 4 μm or less are used. If the particle size is too large, the coating will not be uniform and, as a result, the fluidity and storage stability will not be improved.

As the coating device, any of a rolling type, a fluidized bed type, a mixing type and the like is used, and the water-insoluble fine powder is attached to the surface of the granulated product. For coating, the amount of the water-insoluble fine powder added is preferably 0.5 to 5% by weight based on the granulated product. Specific examples of the water-insoluble fine powder include calcium stearate, magnesium stearate, aluminosilicates such as A-type zeolite, calcium carbonate, magnesium carbonate, magnesium silicate, silicon dioxide (white carbon), and titanium dioxide. By coating in this manner, adhesion between detergent particles is suppressed and blocking due to storage is prevented. In addition, the surface properties are modified by coating with a fine powder to improve the fluidity, surplus water remains in the particles, the solubility is improved, and the solubility in cold water is also practically sufficient. .

Furthermore, the granular detergent obtained as described above is an enzyme,
It may be added as a product as it is by adding a trace amount of ingredients such as fragrances, or sized by immersing it in Marumerizer (Fuji Paudal Co., Ltd.) or by entraining it in a cyclone-like device and bringing it into contact with the wall surface. It is also possible to make the particle shape substantially spherical and to adjust the water content by slightly drying with warm air.

EFFECTS OF THE INVENTION According to the production method of the present invention, unlike the spray drying method conventionally used as a granulation method, there is no high-temperature heat drying step, so that the salt of the sulfonated product of saturated and unsaturated fatty acid ester can be decomposed. It is possible to produce a granular detergent composition having a high bulk density which is suppressed, has excellent powder properties, and has improved rinsability.

Example 1 The following composition was kneaded with a kneader.

Saturated fatty acids _(C 12 _{~C 18)} Sodium salt of sulfonated methyl ester 15 wt% of unsaturated fatty acids _(C 16 _{~C 18)} Sodium salt of sulfonated methyl ester 15 wt% A-type zeolite 25 wt% sodium silicate 15 wt% Sodium carbonate 15 wt% Other additives 5 wt% The obtained intimate mixture pellet (2 cm square) and A-type zeolite were quantitatively fed to a crusher (Okada Seiko, Speed Mill ND-30 type). At this time, cold air of 15 ° C. was introduced together with this crushed material at a ratio of 15 / kg of crushed material. With a crusher, diameter 15 cm
The crushing blade was rotated at 3000 rpm in four stages of cross, and the screen used was a punching metal with a diameter of 2 mm and an aperture ratio of 20%.

Next, the obtained crushed product and A-type theolite having an average primary particle size of 3 μm were put on a rolling drum (D = 30 cmφ, L = 60 cm) at 97: 3.
Was quantitatively fed at a ratio of, and the coated product was discharged at 30 rpm and a residence time of 5 minutes. The properties of the obtained coated product are shown in Table 1 together with the following Examples and Comparative Examples.

Example 2 The crushed product of Example 1 was coated in the same manner as in Example 1 using calcium carbonate having an average primary particle size of 4 μm in a ratio of 97: 3.

Example 3 The crushed product of Example 1 was coated in the same manner as in Example 1 using silicon dioxide having an average primary particle size of 0.3 μm in a ratio of 98.5: 1.5.

Example 4 The following composition was kneaded with a kneader, crushed and coated in the same manner as in Example 1.

Sodium salt 15 wt% unsaturated fatty acids _(C 18 _{~C 20)} Sodium salt 15 wt% A-type zeolite 25 wt% potassium 10 wt% sodium carbonate of sulfonated methyl esters of saturated fatty acids _(C 14 _{~C 18),} sulfonated methyl ester 15 wt% Sodium bisulfite 5 wt% Other additives 5 wt% The crushed product of Example 1 was coated in the same manner as in Example 1 using calcium carbonate having an average primary particle size of 15 μm in a ratio of 95: 5.

Comparative Example 2 The composition shown in Example 1 was made into a granular detergent by a spray drying method.

Comparative Example 3 In Comparative Example 2, the amount of the sodium salt of the sulfonated unsaturated fatty acid ester, which was a liquid, was too large and adhered to the inside of the spray drying tower. Therefore, the composition was adjusted to enable spray drying. The following composition was made into a granular detergent by the spray drying method as in Comparative Example 2.

Saturated fatty acids _(C 12 _{~C 18)} methyl sodium ester of sulfonated salt 12 wt% unsaturated fatty acids _(C 16 _{~C 18)} Sodium salt 8 wt% sodium carbonate 32 wt% Zeolite 12 wt% sodium silicate 5wt the sulfonated methyl ester % Sodium hydrogen carbonate 1 wt% Glauber's salt 24 wt% Method of measuring hydrolysis rate The method of measuring hydrolysis rate shown in Table 1 is shown.

The measurement is performed by a high performance liquid chromatography method (HPLC method) using an RI (differential refractive index) detector. A 0.1 g sample (as an absolute amount) is taken, about 100 ml of 50% ethanol is added, and the pH is adjusted to about 7 with dilute hydrochloric acid. Then, the mixture is heated and dissolved at 60 to 80 ° C for about 10 minutes and filtered, and the filtrate is used as a sample solution for HPLC analysis.

This sample solution is measured by HPLC, and the sodium salt of a sulfonated product of a saturated fatty acid ester whose carbon number of the fatty acid residue is 16
The decomposition rate is calculated from the peak area of the disodium salt based on the following formula.

A: C 16 _- peak area of sulfonated sodium salts of saturated fatty acid ester B: C 16 _- peak area of sulfonated disodium salt of saturated fatty acid ester HPLC conditions Column: Unisil Q C18 Mobile phase: Methanol / H ₂ O (95/5) containing 0.25% cetyltrimethylammonium bromide Detector: RI This decomposition rate is taken as the decomposition rate of sodium salt of sulfonated saturated fatty acid ester .

Claims (1)

[Claims] 1. A detergent composition containing a sulfonated salt of a saturated fatty acid ester and a sulfonated salt of an unsaturated fatty acid ester is kneaded, mixed and then crushed, and then water having an average primary particle size of 10 μm or less. A method for producing a high bulk density detergent composition, which comprises coating with an insoluble fine powder.