DK159553B - PARTICULATED EMERGENCY, SYNTHETIC, WHITE COLORED CLEANING PRODUCT AND PROCEDURE FOR ITS MANUFACTURING - Google Patents

Description

DK 159553 B

in

The present invention relates to particulate synthetic organic cleansers and to a process for their preparation. In particular, it relates to fabric softening cleaners containing bentonite, agglomerated from finely divided bentonite powders on the surfaces of large detergent particles.

Spray-dried detergents are well known and comprise a large amount of particulate, powerful detergent products / sold for use in automatic washing machines.

1C Since clothing washed with such agents can be uncomfortably hard or brittle, especially if dried on a drying line rather than in an automatic dryer, fabric softeners have been used, sometimes in the rinse cycle in the washing process and sometimes in an automatic clothes dryer, to deposit softening material on the surfaces of the laundry. Waxy fabric softeners such as quaternary ammonium halides have also been included in cleansers, but only a small amount of such plasticizers are not discharged with the wash water leaving only 20 slightly deposited on the laundry. Furthermore, such cationic materials react with anionic detergents and fluorescent brightening dyes and are therefore harmful. Bentonite has been used in detergents as a filler and as a plasticizer. Bentonite particles of very small maximum particle size 25 tend to adhere to the material which is washed and provide lubrication sites on the material so as to make it soft by touch. However, various naturally occurring bentonites such as Wyoming bentonite, which may be conveniently used as a plasticizer in detergents, tend to have an impure color or a brownish hue, and may thereby adversely affect the appearance of products containing these bentonites, and this effect is more detrimental. when the bentonite is applied as a surface coating to detergent particles or beads (because agglomeration 55 seems to accentuate benton in the t-color and because the color is not masked by other constituents of the beads). In addition, bentonite, which is usually a very finely divided powder, can be excreted! 2 leach under storage from other larger-sized detergent components unless attached to them. By means of the present invention, these disadvantages are overcome by bentonite added afterwards. In addition, the 5 products invented are less likely to bake together than conventional detergents, have a more uniform appearance than products containing only bentonite agglomerates blended with detergent beads, and have better bead strengths than products in which the clay is incorporated into the blender or afterwards. added as a powder. In an embodiment of the invention, further, the flowability of the product is improved in comparison with similar products containing sticky materials in the detergent composition.

According to the invention, a particulate softening, white-colored detergent product containing detergent particles coated with bentonite is disclosed and the product is characterized in that it consists of a mixture of 10 - 45 wt.% Detergent particles with 20-80 wt.% Impure white bentonite powder, as 2o. adheres to the outside surfaces of the particles, and 90-55% by weight of spray-dried cleaner particles free of such bentonite powder on the surfaces where the bentonite-free particles have sizes in the range of 2.38 mm to 149 µπι, the agglomerate particle sizes are in the range from 2.38 mm to 250 µm, and the individual bentonite particles adhering to the cleaner particles have a size below 74 µm.

The invention also relates to a process for preparing the particulate, fabric softening, synthetic, white-colored detergent product, which is characterized by mixing finely divided bentonite powder and detergent particles with an aqueous sodium silicate solution having a concentration of 2-8% by weight. keeping the surface of the mixture in motion so that new surfaces of the mixed materials are still presented to the spray liquid so that 0.1-0.4% sodium silicate and 2-8% by weight moisture are deposited on the mixture, that mixture

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3, after the aqueous sodium acetate solution has been applied, the bentonite powder is used with a particle size before agglomeration of less than 74 microns, that the scavenger particles are used with such size before agglomeration that the 5 particles range from 2.38 mm to 149 µm, that the bentonite is used in an amount of 20-80% by weight of the fabric softening detergent particles produced and that the sodium silicate is used with a ratio of Na 2 O: SiO 2 in the range of 1: 1.6 to 1: 3.2, 45 wt% coated particles are mixed with 55-90 10 wt% uncoated white detergent particles. Bentonite of such a particle size is used that substantially everything passes through a screen having a sieve opening 74 µm (preferably everything passes through a sieve with a sieve opening 44 µm) and the cleaner particles are spray-dried particles of a builder-containing synthetic organic cleaner with particle sizes in the range of 2.38 mm to 149 µm (most conveniently from 2.00 mm to 250 µm), the sodium silicate preferably having a Na 2 O: SiO 2 ratio of approx. 1: 2.4, the drops of sodium silicate spray liquid have a diameter no greater than 1 mm (preferably in the range of 0.1 * 0.5 mm), and the process takes place in a rotary drum type mixer such as one extending in length at an angle of about 2 to 15 ° with the horizontal plane, the first mixing, spraying and agglomeration and the subsequent mixing taking place in sequence in an upper third part, a middle third part and a lower three part part of the mixer.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic central longitudinal section of a rotary drum type mixer 30 with other equipment usable for carrying out the method of the invention; and FIG. Figure 2 is a cross-section of the rotating drum along line 2-2 showing the spraying of silicate solution onto the upturned particles of detergent and bentonite.

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The detergent particles, which are the basic particles used according to the invention, some of which may be agglomerated with a more finely divided bentonite powder on the surfaces, can all be suitable particles and can be prepared in any of many different ways. However, it is preferred that they be spray-dried particles of sizes from 2.38 mm to 149 µm, preferably from 2.00 mm to 420 µπι. Typically, such products will comprise a synthetic organic detergent which will be either an anionic or nonionic detergent, a builder for the detergent, one or more additives and moisture. Among the various anionic detergents which can be used, usually as their sodium salts, the most preferred are linear higher alkylbenzenesulfonates, higher alkyl sulfates and higher fatty alcohol polyethoxylate sulfates. In the higher alkylbenzene sulfonate 15, the higher alkyl is preferably linear and has on average 11 or 12-15 carbon atoms, e.g. 12 or 13, and is a sodium salt. However, other alkyl benzene sulfonates, having 10 or 12 to 18 carbon atoms in the alkyl groups, may also be used. The alkyl sulfate is preferably a higher alkyl sulfate having 10 to 18 carbon atoms, preferably 12 to 16 carbon atoms, e.g. 12, and is also used as the sodium salt. The higher alkyl ethoxamer sulfates will similarly have 10 or 12-18 carbon atoms, e.g. 12, in the higher alkyl, which is preferably a fatty alkyl, and the ethoxy content will normally be from 3 to 30 ethoxy groups per liter. moles, preferably 3 or 5 - 20. Here again, the sodium salts are preferred. Thus, it will be seen that the alkyls are preferably linear or fatty higher alkyls having from 10 to 18 carbon atoms, the cation is preferably sodium, and when a polyethoxy chain is present in the sulfate, the sulfate is at the end thereof. Other useful anionic detergents include the higher olefin sulfonates and paraffin sulfonates, e.g. the sodium salts in which the olefin or paraffin groups have 10 to 18 carbon atoms. Particular examples of the preferred detergents are sodium tridecylbenzene sulfonate, sodium dodecylbenzenesulfonate, sodium 35-alcohol polyethoxy (3EtO), and hydrogenated tallow-alcohol-sodium salt. In addition to said preferred anionic detergents, others of this well-known group may also be present

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s present, especially in only small quantities compared to those previously described. Mixtures thereof may also be used, and in some cases such mixtures may be better than single detergents. The various anionic detergents are well known and are carefully described on pages 25 - 138 of Surface Active Agent and Detergents, Volume II, by Schwartz, Perry & Berch, published 1958 by Interscience Publishers, Inc.

Although various nonionic detergents with satisfactory physical properties can be used, including condensation products of ethylene oxide and propylene oxide, with each other and with hydroxyl-containing bases such as nonylphenol and oxo-alcohols, it is much preferred that the non-inionic detergent if used , is a condensation product of ethylene oxide and higher fatty alcohol. In these products have! The higher fatty alcohol contains 10-20 carbon atoms, preferably 12-16 carbon atoms, and the nonionic detergent contains from ca. 3 to 20 or 30 ethylene oxide groups per most conveniently, the nonionic detergent is one in which the higher fatty alcohol has approx.

20 12-13 or 15 carbon atoms and containing from 6 to 7 or 11 moles of ethylene oxide. Such detergents are manufactured by Shell Chemical Company and are commercially available under the trade names Neodol ® 23-6.5 and 25-7. Among their particularly appealing properties, in addition to good cleanability in relation to oil dirt on clothes to be washed, is a relatively low melting point, however sufficient above room temperature, so that they can be sprayed on base beads (which may contain builders, but usually no or only slightly detergent) as a solidifying liquid. When nonionic detergents are used and applied to detergent beads as a spray liquid, this spray liquid can be applied exclusively to the beads to be coated with bentonite, or a portion of the nonionic detergent can be spray dried with the builder salt and stable additives. Alternatively, and sometimes preferably (but this is rarely), the nonionic detergent may be sprayed onto the beads with agglomerated bentonite or on a mixture of such beads with product not containing bentonite.

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The water-soluble builder or mixer of builders used can be any of the usual materials used as builders or proposed for this purpose. These include inorganic and organic builders 5 and mixtures thereof. Among the inorganic builders, the preferred are the various phoshates, preferably polyphosphates, e.g. tripolyphosphates and pyrophosphates such as pentane sodium tripolyphosphate and tetrasodium pyrophosphate. Tri * sodium nitrilotriacetate (NTA), preferably used as the mono = 10 hydrate, and other nitrilotriacetates, such as disodium nitrilo * triacetate, are preferred organic builder salts. Sodium = tripolyphosphate, sodium pyrophosphate and NTA can be used in hydrated or anhydrous form. Other water-soluble builders considered effective include the various inorganic and organic phosphates, borates, e.g. borax, citrates, gluconates, EDTA and iminodiacetates. Preferably, the various water-soluble builders will be in the form of their alkali metal salts, either the sodium or potassium salts, or a mixture thereof, but the sodium salt is usually the more preferred. The silicates, preferably the sodium * silicates having a Na 2: SiO 2 ratio in the range of 1: 1.6 -1: 3.0, preferably 1: 2 - 1: 2.8, e.g. 1: 2.35 or 1: 2.4 also serve as water-soluble builder salts, but because of their strong bonding properties, they are useful in supporting agglomeration. The content of silicate in the product will not normally exceed 10 or 15%, with the range 5-15% being possible, preferably 3-7 or 8% when zeolite is not present and 0 - 2 or 5% in the presence of zeolite ( since only small amounts of silicate are used as a binder to hold the bentonite to the detergent or base particles of detergent when zeolite is present). In some cases, it may be desirable afterwards to add free flowing sodium silicate, such as hydrated sodium silicate particles. In addition to the water-soluble builders, water-insoluble builders such as zeolites, especially zeolite A, may preferably be used in hydration.

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7 sered / e.g. containing 20% water, but preferably only partially.

The bentonite used is a colloidal clay (aluminum silicate) containing montmorillonite. The type of bentonite most useful for preparing the basic beads of the invention is that known as sodium bentonite (or Wyoming bentonite), which is usually a light to cream colored or brownish unmanageable powder which forms in water a colloid suspension. 10 having strong thixotropic properties. In water, the swelling capacity of such a clay will usually be in the range of 3 to 15 or 20 ml per day. g, preferably 7-15 ml / g, and its viscosity at a concentration of 6% in water will generally be in the range of 3 to 30 centipoise, preferably 8-30 centipoise. Preferred swelling bentonites of this type are traded under the trade name Mineral Colloid as industrial bentonites by Benton Clay Company, a subsidiary of Georgia Kaolin Co. These materials, which are the same as those previously traded under the trademark THIXO-20 JEL, are selectively excavated and concentrated bentonite, and those considered the most useful are available as Mineral Colloid No. 101, etc., corresponding to THIXO-JEL Nos. 1, 2, 3 and 4. These materials have pH values (6% concentration in water) ranging from 8 to 9.4, maximum free moisture content of approx.

2 5 8% and weights of approx. 2.6, and for the powdered grades, approx. 85% through a 74 μιη sieve. Concentrated Wyoming bentonites are preferred as a component of the present agents, but other bentonites, including the synthetic bentonites (those made of interchangeable calcium and / or magnesium bentonites by treatment with sodium carbonate), are also useful. The particle size can also be reduced so that all the bentonite passes a 44 µm sieve. Although it is desirable to limit the maximum free moisture content, 35 as mentioned, it is more important to ensure that the bentonite used contains sufficient free moisture, most of which is considered to exist between neighboring plates in 8

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the bentonite, to facilitate rapid decay of the bentonite and any neighboring materials in the particles when the particles of detergents containing them are contacted with water such as wash water. It has been found that at least approx. 2%, preferably 5 at least 3% and best approx. 4% or more water must be present in the bentonite from the beginning before it is mixed with the other bead components of the mixer, and this amount must also be present after spray drying or any other drying which is carried out. In other words, drying to the point where the bentonite loses its internal moisture can significantly diminish the utility of the present agents. When the moisture content of the ben-tonite is too low, the bentonite does not contribute satisfactorily to decay of the beads in the wash water.

When the bentonite has a satisfactory moisture content, it can exhibit a percentage amount of interchangeable calcium oxide in the range of from approx. 1 to 1.8, and as far as magnesium oxide is concerned, this percentage may range from 0.04 to 0.41. Typical chemical analyzes of such materials are from 64.8 to 73.0% SiO 2, 14 - 18% Al 2 O 3, 1.6 - 2.7% H 2 O, 1.3 - 3.1% CaO, 2.3 - 20 3 , 4% Fe 2 O 3, 0.8 - 2.8% Na 2 O and 0.4 - 7.0% K 2 O.

Although some additives such as fluorescent brighteners, pigments, e.g. ultramarine blue, titanium dioxide, polyacrylate and inorganic nutrient salts, can be added to the mixer, others, such as perfumes, enzymes, bleaching agents, some staining agents, bactericides, fungicides and flow promoting agents, can often be sprayed or otherwise mixed with the basic beads of spray dried detergent together with any nonionic detergent to be added afterwards and / or independently so that they will not be adversely affected by * the elevated temperatures of the spray drying and also so that their presence in the spray dried beads does not inhibit absorption of nonionic detergent when it is to be sprayed onto the beads afterwards. With stable and usually solid additives, mixing with the starting slurry in the mixer is also often possible. Any less stable additives can also be added afterwards to the agglomerate.

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Of course, water is found in the mixer to serve as a medium for dispersing the various other bead components, and some water, both in free and hydrated form, is found in the product. During drying of the beads, the original moisture content thereof, which will be approx. 25 - 60%, reduced to approx. This moisture content is sufficient for the bentonite in the dried beads (usually less than 10% and preferably nothing) to contain at least 2% and preferably at least 4% moisture. It is preferred to use deionized water so that the content of hardness ion can be very low and so that metal ions which can promote decomposition of any organic materials which may be present in the mixture in the mixer or subsequently added materials are reduced, but in Instead, I5 can usually be used in tap water. Usually, the hardness content of such water will be less than approx. 300 ppm as CaCO 3, preferably less than 150 ppm.

The amounts of the various components in the base beads and 20 in the spray-dried cleaner beads will be such that they result in effective cleaning agents with acceptable flow characteristics, bulk space weight and appearance. Preferably, in most cases, they will be white, although the beads coated with bentonite will often appear darker in color if examined more closely. If desired, a whitening agent such as TiO 9 may be used in an amount of 0.2 to 5% of the bentonite. However, it is within the scope of the invention to use a dye or pigment in the blend in the blender so that the spray-dried beads 30 or beads otherwise produced are colored.

It has been found that satisfactory detergent beads comprising 2 or 5-30 or 35%, preferably 5 or 15-25 or 30%, e.g. 6 - 15% or 35 20 - 25%, synthetic organic detergent, preferably anionic detergent, 20 or 30 - 90%, preferably 30 or 35-80 or 85% and most conveniently 35 or 45 - 70% builder, 0.2 or 0.5 - 35 or 40%, preferably 0.5 or 1-20 or 30% and most conveniently 1 - 10% or 1 - 20% to 10%.

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additives, and 3-20% preferably 4-15% and most preferably 5-12% humidity, e.g. 7 or 8%. Such beads, which can be produced by normal spray drying processes or in any other equivalent manner, will generally have a characteristic spherical or other shape resulting from spray drying and often constitute ideal cores upon which bentonite powder can be agglomerated. They will usually have mass space weights in the range of 0.2 to 0.7 g / l. cm3, such as 0.3 -0.5, e.g. 0.35. The particle sizes thereof will normally be in the range of 2.38 mm to 149 mm, and particles outside this range may be removed by sieving or other suitable means. Preferably, the bead sizes will be from 2.00 mm 15 to 420 mm or 750 mm * and the beads are white or of a different color which may appear adversely affected by the application of the industrial brownish or impure colored bentonite particles to the surfaces thereof, agent is used together thus in an attempt to mimic the original 20 pearl color.

It has been found that when 10 - 60% by weight of the detergent particles have comminuted bentonite powder agglomerated on its surfaces, and 90 - 40% of the detergent particles are without such powder on the surfaces thereof, the human eye does not notice the dark staining of the beads with bentonite. surface and does not detect any harmful cracking of the product, at least not in comparison with products of similar composition, where the bentonite powder is evenly distributed over the spray-dried beads or where bentonite-only agglomerates are used so that consumers do not find them. Invented products harmful discolored. Preferred ranges are 20 - 50% and 30 - 45%, e.g. 40%, for the bentonite surface material, the remainder being uncoated detergent particles. The weight amount of bentonite on the surface of the purifier is 3.5 (the average beads will usually be in the range of 10 or 20 to 80%, preferably 35-65% and most conveniently 40-

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11 60%, e.g. 50%, for the product to be mixed with bentonite-free detergent particles. For the agglomerated particles to be used directly (no mixture with detergent particles), these are in the range of 10 - 30%, preferably 15 - 25%, e.g. 20% of the product. It has been found that since the spray-dried beads are not solid, the application of these relatively large amounts of bentonite does not change the particle sizes drastically, although there may be some increase, such as ca. 5-15 or 30% in bead diameter. The relatively slight increase in bead dimensions does not create precipitation or flow problems, and the presence of the bentonite on the bead exterior seems to help prevent separation of different particle sizes upon storage (compared to similar non-sticky beads with smooth surface). It also does not cause any harmful changes in the mass weight of the product.

The application of the bentonite to the cleanser beads (which in some cases may be inorganic builder beads - as in the case where nonionic detergent is to be added afterwards) can be carried out by standard agglomeration technique and equipment, such as a mixing and agglomeration apparatus. with rotating drum like the one shown in the drawing. One method which has been found to be particularly useful is to mix the desired weight amounts of the detergent beads and finely divided bentonite powder 25 and, during mixing, spray water or preferably spray a dilute sodium silicate solution on the moving surfaces. These sprays may be at room temperature and will gradually be sufficient to prevent harmful lumping of the mixture. The mixing is continued in a known manner until all the bentonite powder is held on the detergent beads, after which the mixture can be stopped and the product can be screened or otherwise sorted by size so that it is within the desired size range. The silicate solution used will have a concentration of 3-7%, such as 4-6%. It is used sufficiently that on the beads it will be from 0.01 to 2%, such as 0.02 - 0.2 or 0.4%. Such concentrations give satisfactory results

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12 agglomeration and surface coating using suitable agglomeration equipment, such as an O'Brien agglomerator, or a conventional inclined drum equipped with spray nozzles, separators, etc. The moisture sprayed on the beads is not too large and is usually 2-8% of the pearl weight, e.g. 2 - 5%, which will be less on the basis of the final product. The resulting product is sufficiently robust to withstand handling, packaging and storage without harmful pulverization and loss of bentonite coating. Also, the silicate concentration is not so high that it prevents dispersion of the bentonite in the wash water when the product is used for laundry. Although it is preferred that silicate is used in the spray liquid for agglomeration, useful products can be obtained by using water alone as an agglomerating agent or by using aqueous solutions of other binders such as gums, resins, surfactants (detergents), but in the absence of such material, the bentonite having bonding properties will usually be sufficiently cohesive to provide coated particles of desired physical stability which are quickly dispersed in the wash water.

In a variation of the present invention, the flowability of the resulting product can be enhanced by incorporating some or all of the most sticky components of the final product into the beads that must have bentonite on the surface. Then, these beads are coated with a protective film of agglomerated finely divided bentonite particles, and the sticky component is buried beneath the bentonite surface, thereby ineffective in preventing free flow. The other particles of 30 detergents which do not contain such a component flow more freely than would be the case if it were also included in their composition. Furthermore, the sticky material can act to promote agglomeration of the bentonite and its adherence to the surfaces of the base particles.

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In another version of the invention, some or all of the synthetic organic detergent, either an aqueous solution of anionic detergent or a liquid nonionic detergent, is actually sprayed on the basic particles of detergent before mixing with the bentonite. This post-spraying of the detergent, instead of incorporating it (or any of it) into the mixer and spray-drying it, improves the spray-drying operation and increases the spray tower production rate. In situations where flowability is not a problem and where relatively large amounts of non-ionic detergent are to be sprayed afterwards on the surfaces of the base beads of detergent, it may of course be unnecessary or undesirable to apply all the detergent or more than a pro rate proportion. thereof, on the beads which have bentonite 15 on the surfaces, but where the flowability is unsatisfactory, this aspect of the invention provides a means of significantly improving it. When at least a portion of the synthetic organic detergent is to be spray dried in the base beads, the beads to be coated with bentonite will usually have at least 20%, preferably 25%, and preferably 50% more detergent than the rest of the beads.

After the beads with bentonite on the surfaces are produced, they can subsequently be mixed with materials to be added afterwards, or these materials can be sprayed onto the bead surfaces, but usually the beads with bentonite on the surface will first be mixed with the rest of the spray-dried cleaner. any material subsequently added can be applied or mixed therewith. Among these materials are enzyme powders, bleaches and perfumes. Alternatively, some of these materials may be applied to or mixed with the various beads or some of them before the bentonite beads on the surface and the other beads are mixed together. It is also possible to add some of the substances afterwards to the detergent beads before applying the bentonite to these beads, but this method is generally not practiced. After mixing the various portions of the present agents, they can be stored for a period of 1 to 24 hours, for example, but usually there is no need for such

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14, and they can then be mixed with any additives, unless this has happened at an earlier time.

They can then be transported to a packing equipment and can be packed, stored and / or shipped.

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The products resulting from the process of the invention will appear, as described above, significantly whiter than similar products in which the bentonite to be used is evenly distributed over all the particles. This phenomenon appears to depend on the amount of the beads and to some extent on the particle size thereof. It is also important that the products invented do not appear brittle even though they contain white and brownish particles. Still, they appear uniform and have a light color. When lesser amounts of bentonite particles are used on the surface than the lower limit of the widest range specified in the foregoing, the darker color of these particles is not necessarily noticeable, but the bentonite content of the product will generally be less than desirable. When a larger amount of bone-tonite particles are applied to the surface than the upper limit of the stated widest range, the product will be clearly darker and impure in color, and its appearance will be unattractive to the average consumer, making it difficult to sell it. . Specific reflectance differences are not stated in the present disclosure because of the varying nature of the naturally available synthetic bentonites and their various color shades, but differences can be seen using a reflectometer such as a Hunter reflectometer, or using a spectrofometer such as one manufactured by General Electric Company. As a rule, however, it is not necessary to use instruments to detect the differences in color, as these are so obvious to the average consumer's eye. When different percentages of detergent are found in the beads with bentonite on the surface and the beads without bentonite 35 p in the surface, and when detergent is applied to the beads to be coated with bentonite, improvements in the flowability of the product are noted, and the products obtained are clearly less

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15 are sticky by touch and are less likely to clump in the box during storage. Such improvements in these properties can be found in standard tests used in the cleaning industry such as flow time, friction angle and compression tests.

It is clear that the properties of the final product are improved without the need for additives to improve color, flow or prevent stickiness. In this way, expenses for such additives and their sometimes undesirable other properties are avoided. Since only part of the detergent beads is subjected to agglomeration, the production times in the agglomeration apparatus are reduced. Thus, both composition and preparation advantages are obtained, and the final product is surprisingly improved compared to a product containing the same total amount of bentonite coating all the particles of detergent.

The following examples illustrate the invention. Unless otherwise stated, all parts are by weight and all temperatures are in ° C.

25 30 35 16

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EXAMPLE 1.

%

Sodium linear tridecylbenzenesulfonate 12 5 Pentane sodium tripolyphosphate, hydrated 34

Sodium silicate (Na 2 O: SiO 2 = 1: 2.4) 7

Sodium sulphate 12

Borax 2

Sodium Carboxymethyl Cellulose 0.5 2q Bentonite (Mineral Colloid 101, 149 µm 7% H2 O)

Perfume 0.5

Humidity 12.0 100.00 15

A detergent of the above composition is prepared by spray drying a mixture of the components with the exception of the bentonite and perfume (and with slightly less silicate added later) having a moisture content of approx. 35% from the mixer in a standard industrial countercurrent spray drying tower under normal conditions where the drying air temperature is in the range of 200 to 400 ° C, to produce spherical beads with a normal particle size distribution in the range of 2.00 mm to 149 // m.

Part of these beads is transferred to an O'Brien agglomerator or similar agglomerator and mixed therein with an equal amount of weight of bentonite, and as the mixture is continued, an aqueous solution (at room temperature) containing an aqueous solution (at room temperature) is sprayed. 5% sodium silicate, with the total amount of spray liquid applied being approx. 0.04 parts. Agglomeration is continued for approx. 20 minutes, during which some moisture evaporates, after which substantially all of the particles range in size from .2.38 mm to 149 µm. Particles outside this range are removed and 1.5 times the weight of the remaining particles (not including added water) of the spray dryers.

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The binder-free detergent beads are then mixed with the bentonite beads on the surface in a drum, where they are rolled over for 20 minutes, after which the product is perfumed and packed in boxes. The spray-dried detergent used herein has a moisture content of approx. 8-10%, but this can be changed by using beads and bentonite with other moisture content and varying the spray liquid accordingly. When the product prepared is compared to a control product prepared in a similar manner, but where the bentonite is coated on all the detergent particles (the total amount of bentonite being the same as in the final product of the invention), it appears to be lighter in color, has a uniform appearance (not stained), is more appealing to the human eye and makes it more acceptable to the consumer. When silicate 15 is omitted from the agglomerating spray liquid, a satisfactory product may also be obtained, but upon aging such a product may be considerably more brittle.

When the procedure described above is varied by mixing 0/3 parts of enzyme powder (Alcalase®, 2 Anton units per g) in pi 11 or powder form (pills in the range of 2.00 mm - 149 µm and powder through a 74 pm) before perfuming, the improvement in the appearance of the product is still evident.

The various products in this example are all satisfactory fabric softening particulate cleaners useful in automatic washing machines for washing dirty clothes.

EXAMPLE 2.

30

A product of the composition of Example 1 is prepared by spray drying two different compositions, one containing 24% sodium linear tridecylbenzenesulfonate and the other containing 13% thereof. The differences are obtained by decreasing or increasing the sodium sulfate content of the respective compositions. The product with the high content

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18 of anionic detergent (and low sulfate content) are more sticky to the touch, and it is this product that is coated with an equal amount of weight of bentonite powder (through a 44 µm sieve) and then mixed with 1.5 times the weight 5 of the resulting agglomerate (which is agglomerated in the same manner as in Example 1) of the beads without bentonite on the surface, which have lower anionic detergent content. The mixture is then perfumed in the usual manner.

The resulting product has improved flowability compared to the product of Example 1, apparently due to the insulating effect of the bentonite particles agglomerated on the surfaces of the high anionic detergent beads. Because of the tackiness of these beads, the amount of silicate solution used can also be reduced, sometimes to half that of Example 1. In addition to providing a product that is more free-flowing, less sticky and less prone to baking upon storage than the products. in Example 1 (which products are acceptable for industrial purposes), the presence of the greater amount of anionic detergent in the bentonite-containing beads promotes faster disintegration and dispersion of the beads in the wash water, which enhancement is supported by the presence of a smaller amount of silicate in the bentonite material on the surface. .

In some cases, as in Example 1, the silicate may be omitted from the agglomeration spray liquid or alternatively equal amounts of other bonding materials such as sodium polyacrylate, polyvinylpyrrolidone or hydroxy may be used instead.

methylcellulose. A further benefit of progress 3 C

the food of this example is that fine bentonite particles, sometimes found together with the bentonite agglomerate, are reduced, which is partly attributable to the sticky detergent.

EXAMPLE 3.

35 ___________

The procedure of Example 1 is varied by reducing the content of anionic detergent in the spray dried beads from

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19 15 to 14% and spray the remaining anionic detergent onto the surface of the portion of the beads to be coated with bentonite particles and into the agglomeration spray liquid. The sprayed material has a solids concentration of approx.

10% in water, and if the manufactured product becomes too sticky, heat and an air stream can be used to reduce the moisture content to reduce the tack to an acceptable level. After mixing the beads with bentonite on the surface with the beads without bentonite on the surface, the resulting detergent has properties comparable to those of Example 2.

EXAMPLE 4.

When the linear sodium tridecylbenzenesulfonate of Example 1 is replaced by hydrogenated tallow alcohol polyethoxy (3 EtO) sulfate, sodium salt, hydrogenated tallow alcohol sulfate, sodium salt, sodium paraffin sulfonate or sodium olefin sulfonate with 16 carbon atoms of the paraffin and olefin groups, parts), products are obtained which are comparable to those of Example 1. This is also the case when the total amount of pentane sodium tripolyphosphate and sodium sulfate is replaced by pentane sodium tripolyphosphate, sodium carbonate, sodium = 25 umbicarbonate, zeolite A or equal parts of a two component mixture thereof. When the amount of bentonite applied to the surface of the beads is varied to 15 and 25%, acceptable products with improved appearance are also obtained, which is also the case when the amount of bentonite particles on the surface changes 30 to 15 and 25%, respectively.

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EXAMPLE 5.

%

Sodium carbonate 22

Sodium bicarbonate 16 5 Zeolite A, hydrated (20% humidity) ^ 32

Fluorescent Detergent (Tinopal) 1.5

Humidity 9.0

Perfume 0.5

Nonionic Detergent ('Keodol * 23-6.5) 19 10 100.00

Detergent beads of the above composition are prepared by spray drying a mixture from a 60% solid bead mixer of the particle sizes shown, comprising all of the described ingredients except for the perfume and the nonionic detergent which is subsequently sprayed onto the surfaces of the beads while they are in motion (though preferably perfume is applied to the bentonite-containing beads after agglomeration). Due to the content of zeolite A 20, the nonionic detergent is absorbed satisfactorily. Then, part of this agent is surface agglomerated with some bentonite powder (44 µm) which appears brownish after coating the particles. After the agglomeration is completed, mix 1 1/2 parts of non-bentonite cleaner,

p C

with the product that has bentonite on the surface. The final product is an excellent plasticizer of the powerful nonionic builder-containing type and has a whiter appearance than a control in which the bentonite is surface agglomerated on all the particles (with the same total concentration of bentonite). The product is a satisfyingly powerful laundry detergent.

When variations are made in the method of preparation, whereby more nonionic detergent, e.g. 1/10 - 1/4 more, spraying on the beads to be coated with bentonite than on the beads not to be coated improves flowability and the product is less sticky.

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21

The foregoing description relates primarily to those aspects of the invention which involve the preparation of a fabric softener with improved color (or appearance) and flowability. Now, preparation of a detergent wherein 5 bentonite is agglomerated on the detergent particles will be described in detail. It will be appreciated that the resulting agent is mixed with detergent particles.

In FIG. 1, there is shown an open, oblique cylindrical rotating drum 11 rotating about an axis which is at a relatively small point angle with the horizontal plane, the rotation being in the direction shown by arrows 13 and 15.

The drum 11 rests on rollers 17, 19 and 21 which rotate in the opposite direction of the drum (counterclockwise, and not clockwise, seen 15 from the left), causing it to rotate as shown.

The rotary drum 11 contains a mixture 23 of spray-dried builder-containing synthetic organic cleanser beads and bentonite powder which are agglomerated into the fabric softener cleanser beads or particles 20 as a result of spraying a dilute sodium silicate solution onto the particles while mixing. The finished agglomerated softener cleaner particles 25 are withdrawn from the drum 11 via a hopper 27. Spray nozzles 29, 31 and 33 are used to produce generally conical sprays of silicate solution, such as those shown by the number 35, which hit the moving mixture. of detergent beads and bentonite powder, and promotes agglomeration of the powder on the surfaces of the beads, although in some cases agglomerates may also be formed from bentonite alone or detergent beads alone (the latter is less common).

In the rotating drum, the right or upper third or similar portion is a mixing zone in which the bentonite and detergent beads are mixed dry, the middle portion is a spray and agglomeration zone, and the lower third or so is one in which no spraying occurs. but in which moist particles and agglomerates are made into a relatively free-flowing product and the desired shape and character of the agglomerate appears.

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22

The foregoing description relates primarily to a rotating drum which is a preferred embodiment of the apparatus used in the practice of the invention, but other equivalent means may also be used.

5 In addition to the rotating drum, supply means are provided for adding the various components of the final product.

Thus, a tank 37 contains sodium silicate solution 39 (as supplied to the spray nozzles 29, 31 and 33 through a conduit 41). A hopper silo 43 contains cleaning beads 45 which are delivered to a hopper 47 by means of a conveyor belt 49. A hopper silo 51 similarly contains bentonite powder 53 supplied to the hopper 47 by means of (conveyor belt 55). Arrows 57 and 59 show the respective directions of movement of these belts.

In FIG. 2, the mixture 23 in the drum 11 is shown as being lifted up on the left wall of the drum which rotates in the direction of the arrow 13. As the mixture 23 descends -20 along the side 61 of the upper wall, the moving mixture of a spray liquid 35 of aqueous silicate solution; sprayed in conical patterns from die 29 and other concealed nozzles 31 and 33, and the mixture is wetted on the surface of the cores of detergent beads and promotes agglomeration of the bentonite with the beads, the more finely divided bentonite powder usually adhering to the surfaces of the larger detergent particles. Thus, constantly renewed sides or carpets of falling particles are brought into contact with the spray liquids, and substantially uniform wetting and application of silicate to the particles is achieved, leading to the production of a more uniform and better agglomerated product.

The detergent particles, bentonite, silicate, additives etc. used in the agglomeration process described are those mentioned above.

When the agglomerated detergent particles with the bentonite on the surfaces thereof are to be used directly, preferably

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23, a silicate solution is used to bond the bentonite to the detergent particles. The aforementioned solution concentrations and amounts may be used, but usually the concentration of the silicate solution will be 2-8%, preferably 3-7% and especially 3-6%, e.g. 4 and 5%. Sufficiently, the silicate from the spray liquid on the beads will be used sufficiently from 0.1 to 0.4%, preferably 0.2 to 0.3%, of the weight of the final product. At such concentrations and amounts, satisfactory agglomeration and surface coating are obtained using the rotary drum or other suitable agglomeration equipment. The moisture that is sprayed on the beads is not too great, usually approx. 3 - 6% by weight of the product. This added moisture can be taken into account by making the cleaner particles more dry.

As with the previously described products, the resulting product is sufficiently robust to withstand handling, packing and storage without damage in g pulverization and loss of bone-tonite coating. The silicate concentration is not so high that it inhibits dispersion of the bentonite in the wash water when the product is used for laundry.

After the beads with bentonite on the surface have been made, they can be mixed with materials to be added afterwards, or these materials can be sprayed onto the bead surfaces. Among these materials are enzyme powders, bleaches and perfumes. Alternatively, some of these materials may be applied to or blended with the base beads or bentonite prior to agglomeration. After the agglomeration is completed

v U

Finally, the products can be stored for a ripening period of 1-24 hours, but as a rule there is no need for such (post-ripening, and the agglomerates can be mixed directly with any additives, unless this has been done before.

The agglomerated beads produced are good cleansers which have considerable softening properties. They are also free-flowing, non-dusty and generally not brittle, like (they have good bead strength and abrasion resistance).

DK 159553 B

EXAMPLE 6.

A slurry is prepared in a mixer comprising 1,009 parts of water, 2,584 parts of a cleaning matrix (ca.

5 37% active ingredient and approx. 20% sodium sulfate, the remainder being water), 841 parts sodium silicate (Na 2 O: SiO 2 = 1: 2.4), 1,315 parts pentane sodium tripolyphosphate, 542 parts anhydrous sodium carbonate, 24 parts sodium sulfate, and 293 parts of an aqueous solution of fluorescent clarifier, means for preventing re-deposition, stabilizer and other minor components in dilute aqueous solution. The mixture is in an industrial cleaner mixer at a temperature of approx.

55 ° C for a period of approx. 10 minutes after adding all the components, adjusting the mixture's solids content to approx. 58 ° C during mixing. The mixture in the mixer is then pumped to a countercurrent spray drying tower where it is forced through 8 10/10 type nozzles at a temperature of 52 ° C under a pressure of approx. 24 kg per cm. The temperatures of the tower are: T ^ = 410 ° C and T2 = 120 ° C. The cleaned beads produced have a moisture content of approx.

7% and the spray rate is approx. 9,000 kg per hour. The beads made are sieved to range in size from 2.00 mm to 250 µm. The beads are white and have a mass space weight of approx. 0.3 g per ml.

25

An equipment which is substantially like the one shown in FIG. 1 and 2 are used to agglomerate finely divided bentonite on the surfaces of the spray-dried cleaning beads described.

To make the desired product with approx. 20% bentonite 30, bentonite powder having a size of 44 µm (containing about 5% moisture) is mixed with the detergent beads in an amount ratio of 76.4 parts of the basic beads to 19.2 parts of bentonite.

3.8 parts of a 5% sodium silicate solution (Na 2 O: SiO 2 = 1: 2.4) is sprayed onto the upturned mixture in the rotary agglomeration and mixing drum using a 6 nozzle syringe (3 is shown in the drawing) ), cler are placed with approx.

1/2 meter gap. The spray pressure is approx. 5 kg per cm2, and

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This gives a misty spray liquid in which the individual droplets have a diameter in the range of approx. 0.1 to 0.5 mm (by weight average). After approx. 8 minutes total mixing in the rotating drum, inclined at an angle of approx. 7®, 5 and where approximately the last third of the drum is free of sieve 1 in cat spray application, the product is continuously removed, then perfumed with 0.2 parts of a suitable perfume and 0.4 parts of enzyme powder mixed therewith. In a variation of the process, the enzyme can be mixed with the product in the drum for the last 10 thirds thereof, with or without perfume.

The resulting product is a particularly useful fabric softening particulate cleaner which can be screened if desired so that it is in the size range from 2.00 mm to 250 µm or from 2.38 mm to 149 µm. The mass weight of the product is approx. 0.35 or 0.4 g per and it comprises approx. 18% sodium dodecylbenzene sulfonate, 25% sodium polyphosphate, 9.5% sodium silicate, 9% sodium carbonate, 10% sodium sulfate, 19% bentonite, 0.4% enzyme powder, 0.2% perfume, 0.1% fluorescent clay 20 ring water and 9% water. The detergent beads are free flowing, non-sticky, strong enough for industrial bargaining, easily dispersible in wash water and of an appealing appearance. In short, the product is an excellent fabric softening powerful acting particulate laundry detergent.

EXAMPLE 7.

The procedure of Example 6 is followed except that 3o the silicate solution used is 3% sodium silicate and the amount of solution applied is 4% of the final product. Flowability, bead strength, freedom from brittleness and abrasion resistance are satisfactory, as is the case of the product of Example 6, and the product is a satisfactorily powerful, fabric softening cleanser. Similarly, when the same amount of a 6% sodium silicate solution is used, good results are obtained. However, when the silicate solution has a concentration of 10%, the product is less added

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26 peaceful, having a clumsy appearance. When only water is used as a spray liquid, an agglomerate is obtained, but it tends to have a higher content of fine particles and is generally less satisfactory than the agglomerates prepared using the sodium silicate solution at a concentration of 2 - 8%. From these experiments and others in which the amount of silicate sprayed solution is varied, it can be concluded that better products are obtained when the amount of spray liquid is approx. 2-8% (based on moisture) of the product and when the silicate deposited in the spray liquid is from 0.1 to 0.4% of the product.

EXAMPLE 8.

The procedure of Example 6 is varied by omitting the anhydrous sodium carbonate from the mixture in the mixer and replacing it with sodium sulfate. Changes can also be made to the locations of the spray nozzles in the agglomerating rotating drum such that the bentonite and the cleaning beads 20 are mixed in the first quarter of the drum, the spraying takes place in the middle half and the subsequent mixing takes place in the last quarter. The resulting product is also a satisfactory fabric softening particulate shaped powerful-acting cleanser just like the cleaners of Examples 6 and 7.

EXAMPLE 9.

Changes are made to the compositions of the mixture in the mixer, the temperatures, the mixing times and the mixing method, and various conditions are used in the spray drying tower to prepare the basic beads of detergent. Variations of -10% and -20% are made in the various constituents of the compositions of Examples 6-8 and in the mixing times, nozzle pressures and other conditions (but these variations are kept within the prescribed ranges) and a good base bead with a mass space weight in the range of 0.3

Claims (2)

Also good products are obtained when, instead of the very finely divided bentonite (44 µm), such as THIXO-JEL No. 1 ("Mineral Colloid" # 1,001), other bentonites such as those manufactured by the American Colloid Company are used. and those produced in Europe, as well as other bentonites which have interchangeable calcium-20 and / or magnesium ions converted to sodium ions by sodium carbon to be treated. Claims. 25 1. Particulate fabric softening, synthetic, white-colored detergent product containing bentonite-coated detergent particles, characterized in that it consists of a mixture of 10 - 45% by weight detergent particles with 20-80% by weight 30 impure white bentonite powder, which adheres to the external surfaces of the particles, and 90-55% by weight of spray-dried cleanser particles free of such bentonite powder on the surfaces where the bentonite-free particles have sizes in the range of 2.38 mm to 149 µm, the agglomerate particles larger in size range from 2, 38 mm to 250 µm, and the individual bentonite particles adhering to the cleaner particles have a size below 74 µm. DK 159553 B Process for the preparation of a batch in cellular fabric softening synthetic white colored detergent product according to claim 1, characterized in that finely divided bentonite powder and detergent particles are mixed together that an aqueous sodium silicate solution having a concentration of 2-8 wt. % is sprayed onto the surface of the mixture while being kept in motion, so that new surfaces of the blended materials are still presented to the spray liquid, leaving 0.1-0.4 wt% sodium silicate and 2-8 wt% 10 moisture on the mixture, the mixture continues after the aqueous sodium sulfate solution has been added, the benzonite powder is used with a particle size before agglomeration of less than 74 microns, that the detergent particles are used with such size before agglomeration that the particles are in the range from 2.38 mm to 149 µm that bentonite is used in an amount of 20-80% by weight of the fabric softeners produced detergent particles, and the sodium silicate is used with a ratio of Na 2 O: SiO 2 in the range of 1: 1.6 to 1: 3.2, then 10-45 wt% coated particles are mixed with 55-90 wt% uncoated white detergent particles. 25 30 35