KR920009044B1 - Detergents - Google Patents

Abstract

A method of producing a free flowing, high active, particulate anionic detergent comprising the step of adsorbing an anionic surfactant acid onto a powdered or granular material such as a phosphate, carbonate, bicarbonate or silicate so as to form an agglomerate. No water is added during the agglomeration stage. The agglomerate may subsequently be coated with a silicate and/or an alkaline salt preferably in a fluidised bed.

Description

cleaning solution

The present invention relates to detergents, in particular free flowing, highly active anionic detergents.

It is an object of the present invention to define a high activity detergent as a detergent comprising at least 12% active substance.

In the present invention, free flowing is defined as a measurable value that is mobilized enough to be repeatedly poured or dispensed.

Washing powders must exhibit, for example, a dust-free, free-flowing, easy-to-handle, well-dissolved and stable copper under normal storage conditions.

Most of the global detergent markets use highly foaming powdery surfactants, most of which are based on the components of the anionic active material.

Various components are added to water to make a slurry, and then the slurry is spray-dried to produce a powder having a normal bulk density of 0.2 to 0.5 gm / ml. Thus, it has been a conventional method to prepare a detergent in powder form. This process is expensive because it requires heat to evaporate the water that is added initially but not needed for the final product.

Another method of making powdered detergents is the so-called 'neutralization method'. Drying neutralization and associated flocculation are normally classified into subdivision processes:

1. Dry adsorption of alkylaryl sulfuric acid on alkaline base surface.

2. Water is added to react alkali and sulfonic acid to form an alkali sulfonate which combines the various components to produce neutralized detergent agglomerates; And

3. Cover the outside of this aggregate with a layer of dry material such as sodium tripolyphosphate, sodium carbonate or sodium silicate.

Initially, the present invention is limited to alkylaryl sulfonic acid in an amount that can be adsorbed onto the surface of various alkali bases without causing excessive aggregation or poor fluidity. For example, the adsorption properties of triphosphates and other adsorbents are claimed to be a function of their surface area. Therefore, sodium triphosphate (STPP) in powder form is more adsorptive than in particulate form. Tables defining the adsorption properties of SPP and other alkalis have been made in the past showing the adsorption properties of various powders with respect to the absorption of alkylarylsulfonic acids such as, for example, dodecyl benzene sulfonic acid (DDBSA). This theoretically limits the amount of active substance that can be made from detergent powders produced by dry neutralization.

Table 1 below shows the limits generally applied to the adsorption of various bases.

TABLE 1

It was previously estimated that approximately 1-2% water needs to be added when neutralizing sulfonic acid with alkali base. This product was not considered stable until the reaction was complete. It was assumed that a desiccant was used to coat the outside of the aggregate and to adsorb free moisture, usually upon hydration of the desiccant, to obtain a free flowing product.

According to a first aspect of the present invention, there is provided a method for preparing a free-flowing, highly active anionic detergent comprising adsorbing an anionic surfactant acid to a powder or particulate material to form an aggregate without adding water in the condensation step. do.

It has been surprisingly found that powders or particle cleaners prepared by the process of the present invention have substantially uniform particles and contain a large amount of surfactant acid that exceeds the maximum content of the surfactant acids of the prior art.

In a second aspect of the invention, there is provided a free flowing, powdered or particulate highly active anionic detergent comprising anionic surfactants adsorbed on a powder or particulate material, wherein the particle composition of the detergent composition is from 248 microns to 1752. Micron.

In a third aspect of the invention there is provided a free-flowing, powdered or particulate highly active anionic detergent composition comprising a surfactant acid adsorbed to a powder or particulate material, wherein the surfactant acid is 12 to 40% by weight of the total composition , Powder or particulate material is contained in 20 to 50% by weight of the total composition.

In a preferred embodiment of the invention, the anionic surfactant acid is adsorbed onto the heat dried powder or particulate matter. In a preferred embodiment of the present invention, the anionic surfactant acid is adsorbed to dry powder or particles heated in a fluidized bed.

In another preferred embodiment, the aggregate so formed is coated with silicate and / or alkali in a fluidized bed. The temperature of the inlet portion of the fluidized bed is preferably 50 ° C. or higher, particularly 85 to 95 ° C.

Suitable anionic surfactant acids can be used. Examples of suitable acids are: alkylarylsulfonic acids, fatty acid sulfonic acids, olefinsulfonic acids, fatty alcohol ether sulfuric acids, fatty methyl ether sulfonic acids, alkalsulfonic acids, especially alkylaryl sulfonic acids or sulfate esters comprising alkyl groups having 9-20 carbon atoms Fatty acid sulfates obtained by groups (in this term alkyl being the alkyl part of the aryl group) or sulfate alcohols having 8-18 carbon atom chains. Particular preference is given to linear alkylbenzene sulfonic acids wherein the average number of carbon atoms of the alkyl groups is from 11 to 13. The amount of the anionic surfactant acid added may be 12% to 40%, particularly 12% to 35%, more preferably 12% to 30% by weight of the final product.

They found that when operated under the conditions of the present invention, they could adsorb at least 50 gm DDBDA / 100 gm STPP powders and thus retained the free flow properties of the final product while significantly exceeding the amount adsorbed according to known methods. .

Powders or particulate matter may contain suitable alkaline materials, alone or in combination with other additional ingredients. Examples of suitable alkaline materials are as follows: for example, sodium phosphate, such as sodium triphosphate, sodium carbonate, sodium bicarbonate, sodium silicate or other similar alkaline materials, including potassium salts or magnesium, the amount of which depends on the weight of the final product. 10 to 95%, in particular 60 to 95%.

Additional components are: for example bleaches such as sodium perborate, preservatives or alkali additives such as sodium silicate, inert fillers such as sodium sulfate, surfactants, optical gloss inhibitors of soil redeposition (e.g. carboxy). Dissolving agents such as sodium methylcellulose, dedusting agents and sodium xylene sulfonates, enzymes, chelating agents, perfumes, emollients, defoamers, bleaching agents, soaps and nonionic actives.

Appropriate devices may be used, but they must be attached for use under appropriate conditions to keep them dry during the flocculation step. Examples of such devices are as follows:

1. An embosser or a stationary or mobile machine with a blade or webbed for mixing powder. This includes twin shell mixers or V mixers, double drums and ribbon or webbed mixers.

2. An air suspension machine in which liquid is sprayed onto the above-mentioned particles to suspend the particles in the air. The particle size increases until the particles are heavy and cannot be suspended, and when the particles cannot be suspended, the particles fall out of the air stream.

3. A device used to flow air similar to liquid in a fluidized column.

The sample powder or particles obtained by this method exhibit the following characteristics:

Particle size

Particle size is greater than or equal to 170 microns and less than or equal to 3 weight percent.

Things less than 250 microns are less than 1 weight percent.

The average particle size is 1100 to 1300 microns.

Bulk Density: 600-720gm / ml without shaking, 730-830gm / ml with shaking

Moisture content: less than 4% W / W

Average friction angle: 37 to 38 °

Tilt angle: min 25 °, max 28 °

Flow rate: 30-41 cc / s (through standard orifice)

Compression degree: 7-15%

Composition of Anion Cleaner Particles

The detergent composition comprises 5-40% by weight, in particular 10-35% by weight, in particular 12-30% by weight, of the anionic surfactant acid, such as alkylaryl sodium sulfate. This detergent composition comprises 20 to 50% by weight, in particular 25 to 45% by weight, in particular 30 to 40% by weight, of powder or particulate matter such as, for example, the alkaline substance sodium triphosphate. The detergent composition may also contain, for example, the following optical components: soda ash, sodium sulfate, sodium carboxymethyl cellulose, optical bleach, metal ion disintegrant, sodium silicate and the like.

For the purposes of the present invention, the friction angle is defined as the horizontal angle to the oblique line of the powder deposit, which deposit is made by pouring the powder directly through the funnel to the center of the circular horizontal surface. This funnel is slowly raised so that the sediment is directly underneath.

The flow rate of the powder is defined as the flow rate in cm per second through an orifice of 1.25 cm in diameter with a smooth PVC funnel extending 10 ° in the vertical direction above the orifice.

The angle of inclination is defined as the minimum angle between the inclined surface and the horizontal plane when the surface is smooth and is a matte medium made of wood and the powder slides through it through gravity. This powder is dispersed in a layer of 20 mm or less in depth on the surface. This surface is slowly raised until sliding is achieved.

The compressibility of the powder is defined as the initial volume fraction (%) lost when the sample is subjected to a compression load, and the compression load is the value over 10 minutes by weight of a 69 mm diameter powder cylinder.

The invention is described in detail in the following examples:

The following mixture was dry mixed and then fed to a horizontal fluid column at a flow rate of 1.83 kg per minute. The initial part of the fluidized column was heated to 80 ° C. or higher and maintained ionicity during the experiment.

* TINOPAL is a trademark of Ciba-Geigy.

As defined below, two liquids were sprayed one after the other over a flowing tower over the flowing powder.

Liquid 1. Spray dodecyl benzene sulfonic acid (DDBSA) at a flow rate of 390 g / minute.

Liquid 2. a solution containing:

This solution was added at a spray rate of 390 g / min. When the alkylaryl sulfonic acid and the silicate solution were added together, the amount was 30.0% w / w.

After treatment, chemical analysis shows that the powder has the following chemical constituents.

This product was dust free and free flowing particle aggregates.

Example 2

The following powder mixture was prepared and used in the same manner as in Example 1.

* TINOPAL is a trademark of Ciba-Geigy.

The composition of the two liquids sprayed along the fluidized column was the same as in Example 1. Liquid 1 was used at a spray rate of 600 g / min. Liquid 2 was used at a spray rate of 390 g / min.

The amount of the alkylaryl sulfonic acid and silicate solution mixture added was 35.0% W / W.

After treatment, chemical analysis shows that the powder has the following chemical components.

The powder produced was a dust free, free flowing particle aggregate.

In this way 35.5% W / W of liquid can be added to the fluidized column, which exceeds the 20% limit disclosed in known methods.

The active substance content was as high as 23.9%, almost double the maximum amount of active substance 12% obtained by the known method using a fluidized bed apparatus.

The amount of alkylaryl sulfonic acid adsorbed on triphosphate and other alkalis far exceeds the previously known degree of adsorption cited in the literature, as shown in Table A.

The theoretical maximum absorption of alkylaryl sulfonic acid in Example 1 was calculated to be 15.075 g of sulfonic acid per 100 g of the original powder mixture. The actual result obtained using the method of the present invention is 21.311 g of sulfonic acid per 100 g of the original powder mixture, which far exceeds the results of the known method.

Similarly, the values for theoretical maximums and actual results in Example 2 are 19.226 g and 32.311 g of alkylaryl sulfonic acids per 100 g of the original powder mixture, respectively.

Regardless of the device, the known drying neutralization method is always limited to a value where water is added and the ratio of the amount of alkylaryl sulfonate to the amount of alkali is constant. This limit is greatly exceeded in the present invention. The present invention provides a method for economically preparing a dust-free, free-flowing, stable high activity anion that is easy to handle and store.

Claims (17)

Alkali metal in a fluidized bed in which 12 to 40% by weight of anionic surfactant acid selected from alkylaryl sulfonic acid, fatty acid sulfonic acid, olefin sulfonic acid, fatty alcohol ether sulfuric acid, fatty methyl ether sulfonic acid, alkanesulfonic acid or mixtures thereof is maintained at a temperature of 80 ° C or higher. To water by spraying and adsorbing on a powder or particulate matter of 20 to 50% by weight containing a substance selected from phosphates, carbonates, bicarbonates, sulfates or silicates of alkaline earth metals or mixtures thereof at a flow rate of 390 g / min to 600 g / min A method of producing a free-flowing, highly active anion cleaner, characterized in that the aggregate is formed without agglomeration and the silicate solution having the following composition is sprayed at a flow rate of 390 g / min to coat the aggregate. The method of claim 1, wherein the powder or particulate matter is heated and dried before adsorption of the anionic surfactant acid. The anionic surfactant acid according to claim 1, wherein the anionic surfactant acid is an alkyl group containing 9-20 carbon atoms and an alkylaryl sulfonic acid containing a sulfonic acid or a sulfate ester group, a fatty acid sulfuric acid obtained by sulphating an alcohol having 8-18 carbon atoms, A method for producing a highly active cleaning agent, characterized in that selected from linear alkylbenzene sulfonic acids having an average number of 11 to 13 carbon atoms in the alkyl group. The method of claim 1, wherein the amount of the anionic surfactant acid is 12 to 35% by weight based on the weight of the final product. The method of claim 4, wherein the amount of the anionic surfactant acid is 12 to 30% by weight based on the weight of the final product. The method according to claim 1, wherein the amount of the alkaline substance contained in the powder or the particulate matter is 60 to 95% by weight. 12 to 40% by weight anionic surfactant acid selected from alkylarylsulfonic acid, fatty acid sulfonic acid, olefinsulfonic acid, fatty alcohol ether sulfuric acid, fatty methyl ether sulfonic acid, alkalsulfonic acid or mixtures thereof and also 60 to 95% by weight of alkali or alkaline earth metals. It is made from 20 to 50% by weight of powder or particulate matter containing a substance selected from phosphates, carbonates, bicarbonates, sulfates or silicates or mixtures thereof, the water content of which is 4% by weight or less and more than 96% by weight of the product of 250 to 1700 A free-flowing, highly active anionic detergent composition having a particle size distribution of microns. 8. The detergent composition of claim 7, wherein the average density of the detergent composition is 1100 to 1300 microns. 8. The detergent composition according to claim 7, wherein the bulk density of the detergent composition is 600 to 720 gm / ml in a untapped state. 8. The detergent composition of claim 7, wherein the bulk density of the detergent composition is tapped between 730 and 830 gm / ml. 8. The detergent composition of claim 7, wherein the angle of repose, defined as the horizontal angle with respect to the deposition slope when the composition is poured, is 36 to 41 degrees. 8. The detergent composition of claim 7, wherein the angle of inclination defined by the minimum angle between the inclined surface and the horizontal plane when the composition slides on the surface of the smooth matte medium is between 25 ° and 28 °. 8. The detergent composition of claim 7, wherein the flow rate of the composition through the standard orifice having a diameter of 1.25 cm is 30 to 41 kPa / sec. 8. The detergent composition according to claim 7, wherein the composition has a compressibility of 7 to 15%, defined as a reduced volume ratio (%) when the composition is subjected to a compression load of 10 kg weight for 3 minutes. 8. The detergent composition according to claim 7, wherein the content of the anionic surfactant acid is 12 to 30% by weight. 8. The detergent composition according to claim 7, wherein the content of the powder or particulate matter is 30 to 40% by weight. 8. The fatty acid sulfuric acid according to claim 7, wherein the anionic surfactant acid is an alkylaryl containing 9-20 carbon atoms and an alkylaryl sulfonic acid containing a sulfonic acid or a sulfate ester group, a fatty acid sulfuric acid obtained by sulphating an alcohol having 8-18 carbon atoms. A detergent composition, characterized in that selected from linear alkylbenzene sulfonic acids having an average number of carbon atoms in the alkyl group of 11 to 13.