JPH0816236B2 - Method for producing high bulk density detergent composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a high bulk density detergent composition containing a sodium salt of a sulfonated product of a saturated fatty acid ester, which has improved solubility and high yield, and is mass-produced industrially. On how to do.

Prior art Sulfonated salts of saturated fatty acid esters have a detergency,
It is a surfactant with excellent hardness and water resistance, and has been attracting attention as an active ingredient of phosphorus-free detergents.

However, the sulfonated salt of a saturated fatty acid ester is susceptible to hydrolysis by heat, and when a granular detergent is prepared by a spray drying method that has been generally used from the past, the ester is decomposed during spray drying, resulting in detergency. There was a problem that it was changed to a disodium salt of low sulfo fatty acid.

Spray-dried products occupy the majority of currently marketed laundry detergents. This detergent is made into bead-shaped hollow particles having an average particle size of about 200 to 800 μm by a spray drying method, and has a low bulk density of about 0.3 g / cc. However, the spray-dried detergent has a problem in that the transportation cost is high, a considerable space is required for storage and display, and it is difficult to store in a general household and it is difficult to weigh it.

On the other hand, there has been proposed a composition and a manufacturing method of a high bulk density granular detergent which eliminates the drawbacks of conventional spray-dried detergents and can be concentrated to be washed with a small amount of detergent (JP-A-60- 72998, 60-72999, 60-9696
8 gazette, gazette 61-69899 gazette, gazette 61-76597 gazette).
According to such a crushing granulation method, it is also possible to prevent the sodium salt of the sulfonated product of a saturated fatty acid ester from being thermally decomposed during the production.

JP-A-60-141091 discloses a method for producing a high-bulk density detergent composition containing a salt of a sulfonated saturated fatty acid ester, by kneading and mixing these detergent raw materials, crushing them, and then averaging the average primary It has been proposed to coat with a water-insoluble fine powder having a particle size of 10 μm or less. However, with this method, it is difficult to industrially obtain a large amount of raw material powder.

Japanese Patent Application No. 61-80917 discloses that a dry powder obtained by drying a slurry containing an anionic surfactant and zeolite is kneaded and mixed with another detergent raw material to form a high bulk density detergent. Is proposed. In that example, a dry powder obtained by drum-drying a sulfonated product of a saturated fatty acid ester and zeolite and kneading and mixing sodium silicate and a sodium salt of a sulfonated product of an unsaturated fatty acid ester to crush and granulate. are doing.

In addition, looking at the alkali builders that have been used up to this point, the detergency of the potassium salt type alkali builders is significantly reduced, insolubilization occurs over time with sodium silicate, and the solubility is reduced with sodium carbonate. Was given.

However, an alkali builder is indispensable in order to fully exert the high detergency of the sodium salt of the sulfonated saturated fatty acid ester. Among them, sodium carbonate is an industrially suitable builder because it is comprehensively superior in terms of performance and price.

OBJECT OF THE INVENTION The present invention provides a method for producing a high bulk density detergent composition containing a sodium salt of a sulfonated product of a saturated fatty acid ester, which has significantly improved solubility and can be mass-produced with a good appearance and shape. The purpose is to

Composition of the Invention A method for producing a high bulk density detergent composition of the present invention was obtained by drying a slurry of a detergent raw material composition containing a sodium salt of a sulfonate of a saturated fatty acid ester, zeolite and sodium carbonate or further sodium bicarbonate. Dried product and nonionic surfactant, sodium salt of sulfonated saturated fatty acid ester / nonionic surfactant = 1.0 ~
Mix and knead uniformly under strong shearing force in the range of 3.5 (weight ratio), and then use the cutter mill type crusher with screen classification ability to knead the kneaded product with a large screen hole diameter. The feature is that the crushers are sequentially supplied to small crushers to perform multi-stage crushing.

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

In the present invention, first, a dried product containing a sodium salt of a sulfonated saturated fatty acid ester, zeolite, and sodium carbonate (alkali builder) is prepared. Further, sodium bicarbonate can be added as an alkali builder. By incorporating sodium bicarbonate, the pH can be adjusted and the decomposition of the sodium salt of the sulfonated saturated fatty acid ester can be controlled.

As a sulfonated product of a saturated fatty acid ester, a salt of a sulfonated product of a lower alkyl ester of a saturated fatty acid having a carbon number of a fatty acid residue of 12 to 20 is representative, and a lower alkyl group having a carbon number of 1 to 6 Is appropriate. Of these, fatty acid residues having 14 to 18 carbon atoms and lower alkyl groups having 1 to 2 carbon atoms are preferable. Further, a sodium salt is used as the salt.

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.

Zeolite is preferably contained in the dried product in an amount of 20 to 35% by weight.

Sodium carbonate and sodium bicarbonate are used as the alkali builder. It is desirable that sodium carbonate is contained in an amount of 25 to 45% by weight and sodium bicarbonate is contained in an amount of 0 to 20% by weight in the dried product.

If necessary, the following optional components may be contained. For example, alkyl sulfate (AS), polyethoxyalkyl sulfate (AES), alkylaryl sulfonate (LAS), olefin sulfonate (OS). ), An anionic surfactant such as soap; a chelate builder such as sodium citrate, sodium ethylenediaminetetraacetate, sodium nitrilotriacetate; a fluorescent agent, a dye and the like. Each of these components can also be added in the kneading step. Also, bleaching compositions, enzymes, flavors and the like may be added to the final product.

Spray drying can be performed by a conventional method, for example,
It is carried out by drying a detergent slurry containing 50 to 100 parts by weight of water with respect to 100 parts by weight of the above-mentioned detergent components in a countercurrent spray drying tower. The pH of the slurry is adjusted to prevent hydrolysis of the sodium salt of the sulfonated saturated fatty acid ester.
Is preferably 12 or less.

The water content of the obtained spray-dried product is preferably 10 parts by weight or less with respect to 100 parts by weight of the above-mentioned detergent component, from the viewpoint of powder physical properties in consideration of handling in a subsequent step.

Then, the dried product and the nonionic surfactant are uniformly mixed and kneaded to obtain a kneaded product.

The following are preferably used as the nonionic surfactant.

(1) An alcohol EO addition type nonionic surfactant obtained by adding ethylene oxide (EO) to a primary or secondary alcohol having an average carbon number of 8-18.

(2) For primary or secondary alcohols with an average carbon number of 8-18
Alcohol EO-PO addition type nonionic surfactant to which EO and propylene oxide (PO) are added.

(3) A fatty acid EO-added nonionic surfactant obtained by adding EO to a fatty acid ester.

The alcohol EO addition type nonionic surfactant preferably has an EO addition mole number of 8 to 30. Alcohol EO-PO
Addition-type nonionic surfactants have an average EO content of 8-20 mol, PO
Is preferably added in an average of 3 to 15 mol. Fatty acid EO
The addition-type nonionic surfactant is preferably one to which EO is added in an average of 8 to 30 mol, and the fatty acid ester is preferably a saturated or unsaturated fatty acid ester having 12 to 18 carbon atoms.

Further, (b) the nonionic surfactant is (a) / (b) = 1.0 to 3.5, preferably 1. with respect to the sodium salt of the sulfonated product of the (a) saturated fatty acid ester in the dried product.
It is necessary to mix in a ratio of 2 to 2.5. This value is 1.
When it is less than 0, the amount of the nonionic surfactant is too large, so that gelation occurs on the surface of the detergent particles during dissolution, the dissolution rate is lowered, and the adhesiveness is increased, resulting in deterioration of manufacturability.
On the other hand, if it exceeds 3.5, the solubility improving effect is insufficient.

In order to fully exert the effect of improving the solubility by the nonionic surfactant, it is necessary to microscopically uniformly mix the sodium salt of the sulfonated product of the saturated fatty acid ester in the dried product and the nonionic surfactant. Is. Therefore, the dried product and the nonionic surfactant are uniformly mixed and kneaded under a strong shearing force. This mixing / kneading can be performed by a kneader, and a continuous kneader is preferable. In particular, in the latter crushing step, since it is preferable to pelletize and supply the kneaded product in order to reduce the load on the crusher, a kneader having both functions of uniform kneading and pelletization is preferable. For example, it is commercially available as KRC Kneader from Kurimoto Iron Works Co., Ltd.

A usual extruder is insufficient in terms of uniform mixing although pressure is applied, and a sufficient solubility improving effect cannot be obtained. The extruder can be used as an auxiliary device for pelletizing after making the close kneaded product.

By kneading and mixing the nonionic surfactant, the solubility of the obtained high bulk density detergent is remarkably improved, and
It is now possible to use sodium carbonate as an alkali builder. Furthermore, the rinsability of the detergent composition is also improved by adding a nonionic surfactant.

The kneaded product thus obtained is subjected to multi-stage crushing by using a cutter mill type crusher having a screen classification function and successively supplying the crusher having a large screen hole diameter to a crusher having a small screen hole diameter.

By sequentially supplying from a cutter mill type crusher with a large screen hole diameter to one with a small hole diameter and performing multi-stage crushing until it becomes a granulated product of the target particle size, the average particle ratio before and after the crusher is charged becomes small, It is not subjected to excessive crushing, the amount of fine powder is reduced, and the yield is improved.

In addition, due to the fact that it does not undergo excessive crushing and it receives many circular center effects (size adjustment) in the crushing chamber, it has a sharp particle size distribution and an improved shape with almost no flat particles or acicular particles. This is an industrially effective method as a granulation method for a high bulk density detergent having a high commercial value, since a crushed granulated product is obtained.

Further, the crushing capacity can be improved as compared with the case where the same number of crushers as those used for the multi-stage crushing granulation are arranged in parallel as the conventional one-stage crushing method. In this case, in each stage of the crusher, set the average particle size ratio at the entrance and exit of the crusher to an appropriate value to obtain the required degree of crushing (smaller particle size).
By allocating the amount to each stage, the crushing capacity can be improved even more effectively.

Prior to crushing the kneaded product with a cutter mill, it is suitable to pelletize the kneaded product by the above-mentioned continuous kneader or extrusion molding. Diameter pellets 2 to 10 mm ^phi are suitable, preferably 4 to 7 mm ^phi. If the pellet diameter is too small, an increase in the extrusion pressure may cause a trouble such as deformation of a die attached to the extruder. On the other hand, if the pellet diameter is too large, the load on the crusher increases. The length of the pellet is preferably 5 to 30 mm, and preferably 5 to 15 mm, in consideration of adhesion to the pellet cutting knife and load on the crusher.

The pellets are crushed in multiple stages by a cutter mill type crusher having a classification screen, and crushed and granulated.

The average particle size of the final crushed granulated product is preferably 300 to 1500 μm, and more preferably 500 to 1000 μm. If the particle size is large, the solubility in laundry will be delayed, and problems such as cloth adhesion and detergency will occur.

A cutter mill type crusher has multiple stages of rotary crushing blades and discharges crushed materials through a 360 ° release screen. For example, it is commercially available as New Speed Mill (Okada Seiko Co., Ltd.) . An arbitrary upper limit particle diameter can be set by adjusting the opening diameter of the screen.

The screen is not particularly limited, such as a wire mesh type, a herringbone type, or a punched metal type, but punched metal is preferable in consideration of the screen strength and the shape of the crushed material.

The crushing capacity in the multi-stage crushing of the high bulk density detergent is preferably large so that the crushing machines are connected in series and common to each stage. To achieve this,
It was found that there is an optimum value for the ratio of the average particle size at the crusher inlet and outlet obtained by selecting the screen hole diameter.

When the average particle size at the start of the crushing process and the desired average particle size of the crushed and granulated material are set, the number of crushing stages is naturally determined in accordance with this. At that time, it is more effective if the relationship between the screen hole diameter and the average particle diameter of the obtained crushed material is previously obtained by an experiment.

Further, as can be seen from the above relationship, since the powder surface area is small and the load applied to the crusher is small with a large particle size,
The ratio of the average particle diameter at the inlet-outlet can be widened. Therefore,
In the multi-stage crushing, it is desirable to reduce the crushed particle size as much as possible in the crusher in the upper stage.

For multi-stage crushing, it is possible to install a sieve at the discharge port of the crusher for each stage and supply only the crushed material of the desired particle size to the crusher of the next stage. It is disadvantageous in terms of area increase. Therefore, the discharged material (crushed material) from the first-stage crusher is used as it is in the second-stage (and further 3
The direct connection type for supplying to the crusher of the second stage and thereafter) is preferable.

At the time of crushing, it is preferable to add a crushing aid. The crushing aid is generally known as a grinding aid, and when added in a small amount to the crusher, it has the effects of reducing the crushing power, improving the crushing particle size, and improving the properties of the crushed product. .

The particle size of the crushing aid is suitably 50 μm or less, preferably 20 μm or less. The addition amount is 0 with respect to the crushed amount.
5-10% by weight is preferred. As the type of crushing aid,
Aluminosilicates such as stearates, A-type zeolites,
Calcium carbonate, magnesium carbonate, magnesium silicate, silicon dioxide, titanium dioxide, finely ground sodium carbonate, sodium sulfate are preferred. These crushing aids adhere to the surface of the crushed material and reduce the surface activity of the crushed material, thereby preventing adhesion to the crusher, reducing the crushing power, and improving the fluidity of the crushed material. Can be

As a method of adding the auxiliary agent, there are a method of mixing before crushing in advance, a method of adding all the required amount in the first stage of the multistage crushing at once, and a method of dividingly adding each stage. Any of these may be selected, but batch addition is desirable in view of the effect of the auxiliary agent and economic efficiency. Further, by forming a system in which the crushers are directly connected to each other and each stage is hermetically closed (closed direct connection type), the loss of the auxiliary agent is reduced, and it is possible to effectively operate with a small amount of the auxiliary agent added.

It is desirable to introduce cold air into the crusher in order to prevent the crushed material from being softened by the crushing heat and attached to the crusher. The cold air temperature is suitably 10 to 25 ° C, preferably
15-20 ° C. Also, the appropriate amount of cold air is 0.1 to ⁵ m ³ / kg (crushed material). If the amount of the cold air is too large, the temperature of the crushed material is remarkably lowered, and the crushed material becomes hard and brittle.

As a method for introducing the cool air, any of a collective introduction of a required amount to the first stage and a divisional introduction to each stage may be used. It is economically advantageous to recycle the cold air discharged from the crusher after separating it from the powder.

The resulting crushed granulated particles may be coated with a water-insoluble powder to further improve the powder properties.

Further, sodium bisulfite may be used as a coating agent for the purpose of preventing hydrolysis of the sodium salt of the sulfonated product of saturated fatty acid ester. The coating agent is not limited to one type, and may be a combination of type A zeolite and sodium bisulfite.

Effects of the Invention According to the present invention, in a detergent composition using a sodium salt of a sulfonate of a saturated fatty acid ester having high detergency and excellent hard water resistance, the solubility in cold water is good, and
It is suitable as an industrial production method because it can mass-produce a high-density bulk granular detergent with a product shape close to a sphere and having excellent powder properties and appearance in a high yield.

Example 1 A high-bulk density detergent having the composition shown in Table 1 below was produced. Of this composition, the sodium salt of sulfonated saturated fatty acid methyl ester, soap, sodium carbonate 20
/ 30, A / zeolite 20/25, sodium bicarbonate were adjusted to have a slurry water content of 55%, and then dried to a water content of 7% using a countercurrent spray drying tower. The temperature of the hot air used was 360 ° C.

The obtained spray-dried product has an average particle size of 350 μm and a bulk density of 0.2.
The fluidity was also good at 5 g / cc and the angle of repose of 45 °.

Then, the spray dried product, a nonionic surfactant containing a blue dye (a primary alcohol having 12 to 13 carbon atoms with 15 mol of ethylene oxide added) and 10/30 of sodium carbonate were continuously kneaded (Kurimoto Tekko Co., Ltd.). Introduced into KRC Kneader # 2) to obtain a dense and uniform kneaded product.

Cold water at 5 ° C. was flowed through the kneader jacket to remove kneading heat and the like. The temperature of the obtained pellets was 40 ° C.

Lower outlet, perforated plate having 80 a hole diameter of 5 mm ^phi (thickness 10 mm) was placed, and a cylindrical pellets of approximately 5 mm ^phi × 10 mm and kneaded product. This pellet has a uniform blue color, and it can be seen that the nonionic surfactant and the spray-dried product, that is, the sodium salt of the sulfonated product of saturated fatty acid methyl ester are uniformly mixed.

The obtained pellets were introduced into a crusher (New Speed Mill ND-10 type, Okada Seiko Co., Ltd.) together with cooling air at 15 ° C. in an amount twice the weight ratio. At this time, 5/25 of A-type zeolite having an average particle size of 1 μm (primary particle size) was simultaneously added as a grinding aid.

The crusher has a cutter with a length of 15 cm in four stages of cross, rotates at 3000 rpm, and the screen is made of 360 ° punching metal. This crusher is connected in three stages continuously,
The discharge (crushed material) from the first-stage crusher is supplied to the second-stage crusher, and then similarly to the third-stage crusher, and the multi-stage (3
Dan) Crushed. The hole diameter of punching metal is the first step: 3.5
mm ^φ , second stage: 2 mm ^φ , third stage: 1.5 mm ^φ .

The particles that passed through the crusher in three stages were separated from the cooling air to obtain a product (high bulk density detergent).

The detergent composition, manufacturability and product properties are shown in Table 1 below.

Example 2 and Comparative Examples 1-2 A high bulk density detergent was prepared in the same manner as in Example 1 except that the ratio of the nonionic surfactant to the sodium salt of the sulfonated saturated fatty acid ester was changed as shown in Table 1. A composition was produced. The properties are shown in Table 1. The amount of fluctuation of the nonionic surfactant was adjusted with a soap which also has a defoaming effect.

Examples 3 to 4 The ratio of the nonionic surfactant to the sodium salt of the sulfonated saturated fatty acid ester was changed as shown in Table 1, and the same procedure as in Example 1 was performed until spray drying.

This spray-dried product, nonionic surfactant with blue dye added (15 mol of ethylene oxide added to primary alcohol having 12 to 13 carbon atoms) and sodium carbonate
30 and 5/25 of A type zeolite were introduced into a continuous kneader (Kurimoto Iron Works, KRC Kneader # 2 type) to obtain a dense and uniform kneaded product. Further, a high bulk density detergent composition was produced in the same manner as in Example 1 except that 6/30 of sodium carbonate having an average particle size of 30 μm was added as a grinding aid instead of type A zeolite. The properties are shown in Table 1. The fluctuation of the nonionic surfactant was similarly adjusted with soap having a defoaming effect.

Example 5 The same as Example 1 except that the ratio of the nonionic surfactant to the Na salt of the sulfonated product of the saturated fatty acid ester was changed as shown in Table 1 to 0 sodium bicarbonate in the spray-dried product. To produce a high bulk density detergent composition. The properties are shown in Table 1. The fluctuation of the nonionic surfactant was similarly adjusted with soap having a defoaming effect.

The product shapes of the granular detergents obtained in Examples 1 to 5 were all spherical with rounded corners.

Comparative Example 3 A high bulk density detergent was produced so as to have the composition shown in Table 1 below. Of this composition, the sulfonated sodium salt of saturated fatty acid methyl ester, soap, sodium silicate, 20/25 of sodium carbonate A type zeolite has a slurry water content of 55%.
After adjusting so that the water content is 7%.
Dried up. The hot air temperature used was 320 ° C.
Then, the same operation as in Example 1 was performed to produce a high bulk density detergent composition. This product had a problem that the residual rate of the sodium salt (SF) of the sulfonated product of a saturated fatty acid ester, which is a surfactant, was low. The results are shown in Table 1.

Further, the dissolution rate and the manufacturability in the table and the residual ratio (SF residual ratio) of the salt of the sulfonated saturated fatty acid were evaluated as follows.

Dissolution rate Put water 1 at 25 ° C in a beaker and insert a cell for measuring conductivity into it. Next, 0.83 g of each high-bulk density detergent composition was added to water, stirred at a speed of 250 rpm using a low-speed stirrer, and 90% of the added detergent particles were dissolved, and the time was measured from the change in conductivity, and then dissolved. It was speed. Here, as the conductivity meter, HORIBA CONDUCTIVE METER DS-8F type was used.

Manufacturability The following criteria were evaluated.

○: The capacity is 100 kg or more and there is no adhesion to the device.

Δ: Adhesion to the device is slightly recognized with a capacity of 50 kg to 100 kg.

X: Adhesion to the device with a capacity of 50 kg or less.

Method of measuring residual ratio The total amount of surfactant is determined by the methylene blue back titration method, and the amount M of sodium salt of the sulfonated saturated fatty acid methyl ester is determined from the preset blending ratio of the surfactant. The detergent composition is then treated with a 90% ethanol solution at pH 11,50 ° C. to separate the di-salt as insoluble matter. This disalt is dissolved in a 50% ethanol solution, the amount of disalt S is determined by the methylene blue back titration method, and the sodium salt residual ratio (SF of the sulfonated product of saturated fatty acid methyl ester is calculated by the following formula: SF
Residual rate).

SF residual rate (%) = [(MS) / M] x 100 Examples 6 to 9 With respect to the detergent compositions having the same composition as in Example 3 except that the kind of the nonionic surfactant was changed as shown in Table 2, products were prepared in the same manner as in Example 1. The properties are shown in Table-2.
Shown in

Comparative Example 4 In the same composition as in Example 1, the continuous kneader was changed to an extruder (Fuji Paudal: Peretta, double EXD-60 type), and other steps were performed in the same manner as in Example 1 to produce a product. did. The color of the extruded granules was not uniform, and adhesion occurred after the second stage of the crusher, and stopped after 10 minutes. The properties of the collected small amount of sample are shown in Table 3 below.

Examples 10 to 11 and Comparative Example 5 With the same composition as in Example 1, the crushing process was changed as follows, the crusher was operated at the upper limit of the capacity, and the other processes were the same as in Example 1. I made a product in. The properties are shown in Table-3.

Example 10: Three-stage crusher Example 11: Two-stage crusher The screen hole diameters are 2.5 mmφ and 1.5 mmφ.

Comparative Example 5 The crusher has a 1-stage screen hole diameter of 1.5 mmφ.

In addition, the difference in particle shape due to the difference in crushing process is also shown in Table-3.

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Claims (1)

[Claims] 1. A dried product obtained by drying a slurry of a detergent raw material composition containing a sodium salt of a sulfonate of a saturated fatty acid ester, zeolite and sodium carbonate, or sodium bicarbonate, and a nonionic surfactant are saturated. Sodium salt of sulfonated fatty acid ester / nonionic surfactant = 1.0 to 3.5 (weight ratio), uniformly mix and knead under strong shearing force, and then screen classify the kneaded product. A method for producing a high-bulk density detergent composition, which comprises using a cutter mill type crusher having a function and sequentially supplying the crusher with a large screen hole diameter to a crusher with a small screen diameter to perform multi-stage crushing.