SE466263B - PREPARED TO MANUFACTURE A SOFT-SOILING PARTICULAR, SYNTHETIC, ORGANIC DETERGENT COMPOSITION - Google Patents

Description

466 265 10 15 20 25 30 35 which effect is more offensive when the bentonite is applied as a surface layer to the detergent particles or grains (because the agglomeration seems to accentuate the color of the bentonite and also because the color is not masked by other constituents in the grain). Likewise, the bentonite, which usually consists of a very finely divided powder, can separate during storage from other particles in the larger size detergent composition if it is not adhered to them. In practicing the present invention, these disadvantages of subsequently added bentonite can be eliminated. In addition, the products obtained according to the process of the invention have less tendency to bake together than conventional detergent compositions and a more homogeneous appearance than products containing only bentonite agglomerates in admixture with detergent grains, and the strength of the grains is better than in the case of products in which the clay has been incorporated into the mixture or added afterwards in the form of a powder. In accordance with an object of the invention, there is provided a process which provides a product with a further improved flowability, compared to the corresponding products in which the detergent composition comprises tacky substances.

The present invention also relates to a process for producing a finely divided synthetic organic detergent product which means that finely divided bentonite powder and particles of larger size of a detergent composition are agglomerated so that the bentonite powder adheres to the surface of the detergent particles. While agglomeration is effected by stirring. aqueous solution of sodium silicate.

In accordance with the main object of the invention, there is provided a method of preparing a fabric softening particulate, synthetic, organic detergent composition causing bentonite powder to adhere to the surfaces of the detergent composition particles by mixing a minor f; 46 15 263 amount of a finely divided bentonite powder with a larger amount of detergent particles of larger size, sprays the particle surfaces in the mixture, while this is in motion so that new surfaces of the mixed materials are continuously exposed to the spray liquid, with a minor amount of an aqueous sodium silicate solution having a concentration in the range of 2 to 8% by weight in such a quantity that the spray liquid deposits between about 0.1 and 0.4% by weight of sodium silicate and about 2 to 8% by weight. % water on the mixture, subject the mixture to continuous stirring after the addition of the aqueous sodium silicate solution and remove agglomerated particulate detergent with bentonite powder retained on its surface. Preferably, the bentonite used has such a particle size that substantially the entire amount passes through a No. 200 sieves (mesh size 0.074 mm) according to the American sieve series (and even more preferably through a No. 325 sieve: mesh size 0.044 mm), the particles of the detergent composition consist of spray-dried particles of a prepared organic detergent composition which have such a particle size that they passes through No. 8-100 sieves (mesh size 2.38-0.149 mm: or even better by No. 10-60 sieves: mesh size 2.00-0.25 mm), the sodium silicate has a Na 2 Si ratio of about 1: 2.4, the droplets in the sodium silicate spray liquid have a diameter not exceeding 1 millimeter (more preferably in the range 0.1-0.5 mm), and preferably the process is carried out in a rotating drum of the mixer type , as in a longitudinal drum with a horizontal angle of between 2 and 15 °, the initial mixing, the spray agglomeration and the subsequent stirring taking place continuously in an upper third, a middle third and a lower third of the mixer, respectively.

The present invention, including the embodiment thereof, is clear from the following description in combination with the drawing, in which Fig. 1 shows a schematic view of a central longitudinal section of a rotating drum of mixer type, together with another equipment which can be used in the application of the method according to the invention: and Fig. 2 shows a transverse section of the rotating drum along the plane 2-2 and illustrates the spraying of the silicate solution on the tumbling particles of detergent composition and bentonite.

The particles of detergent composition which constitute the base particles used according to the invention, and some of which can be agglomerated with a more finely divided bentonite powder on the surface thereof, may consist of any suitable particles and be prepared in any suitable manner. However, it is very suitable that they consist of spray-dried particles with sizes within the sieve range No. 8-100, preferably 8 or 10 to 60 and more preferably 10 to 40 or 60, according to the American sight series. Typically, these products comprise a synthetic organic surfactant which is to be either an anionic or nonionic surfactant, a detergent, adjuvant (s) and water. Among the various anionic surfactants that can be used, usually in the form of sodium salts, the most preferred are straight chain higher alkylbenzene sulfonates, higher alkyl sulfates and higher fatty alcohol polyethoxylate sulfates. In the higher alkylbenzene sulfonate, the higher alkyl chain is preferably straight with an average of 11 or 12 to 15 carbon atoms, for example 12 or 13 carbon atoms, and it is a sodium salt. However, other alkylbenzene sulfonates having 10 or 12 to 18 carbon atoms in the alkyl group may also be used. The alkyl sulphate is preferably a higher fatty alkyl sulphate having 10 to 18 carbon atoms, preferably 12 to 16 carbon atoms, for example 12 carbon atoms, and this is also used in the form of the sodium salt. Likewise, the higher alkyl ethoxylate sulfates should have 10 or 12 to 18 carbon atoms, for example 12 carbon atoms, in the higher alkyl chain, which is preferably a fatty alkyl, and the ethoxy content should normally be between 3 to 30 ethoxy groups per mole, preferably 3 or 5 to 20. Again, the sodium salts are preferred. Thus, it appears that the alkyl groups are preferably straight or higher fatty alkyl groups having 10 to 18 carbon atoms, that the cation is preferably sodium and that when a polyethoxy chain is present the sulfate group is present at the end thereof. Other useful anionic surfactants are higher olefin sulfonates and paraffin sulfonates, such as those sodium salts in which the olefin or paraffin groups have 10 to 18 carbon atoms. Particular examples of the preferred surfactants are sodium tridecylbenzenesulfonate, sodium dodecylbenzenesulfate, sodium tallow alcohol polyethoxy (3EtO) sulfate and sodium hydrated tallow alcohol sulfate. In addition to the preferred anionic surfactants mentioned, other compounds from this well known group may also be present, especially in minor amounts relative to those described above. Mixtures thereof can also be used and in some cases the mixtures may be superior to the individual surfactants. The various anionic surfactants are well known in the art and are described in detail on pages 25-138 of the publication "Surface Active Agent and Detergents", vol. II, by Schwartz, Perry and Berch, published in 1958 by Interscience Publishers, Inc. Although various nonionic surfactants having satisfactory physical properties may be used, including condensation products of ethylene oxide and propylene oxide with each other and with hydroxyl-containing bases such as nonylphenol and the oxotype of alcohols, it is preferred that the nonionic surfactant, if present, be a condensation product of ethylene oxide and higher fatty alcohol. In these products the fatty alcohol has 10 to 20 carbon atoms, preferably 12 to 16 carbon atoms, and the nonionic surfactant contains between about 3 and 20 or 30 ethylene oxide groups per mole, preferably from 6 to 12. Most preferably it should 466 10 15 20 25 30 The nonionic surfactant may be one in which the higher fatty alcohol has about 12 to 13 or 15 carbon atoms, and which contains between 6 and 7 or 11 moles of ethylene oxide.

Such surfactants are manufactured by Shell Chemical Company and are available under the trademark Neodol ° 23-6.5 and 25-7.

One of their particularly appealing properties, in addition to good cleaning ability with respect to oil stains on clothes to be washed, is a comparatively low melting point, which, however, is considerably above room temperature, so that they can be sprayed on the base grains (which may contain laundry detergents but usually a little or no surfactant) in the form of a solidifying liquid. When nonionic surfactants are used and applied to the detergent grains as a spray liquid, the spray liquid can be applied only to the grains to be coated with bentonite, or part of the nonionic surfactant can be spray dried together with the detergent salt and stable adjuvants. Alternatively and sometimes preferably (but this is rare), the nonionic surfactant may be sprayed onto the agglomerated concrete-coated base grains or onto a mixture of such grains and non-concrete product.

The water-soluble detergent salt used or the mixture of detergent salts may consist of one or more of the conventional materials used as detergent or suggested useful as such.

These include inorganic and organic detergent salts and mixtures thereof. Of the ophthalmic detergent salts, the various phosphates, especially the polyphosphates, such as tripolyphosphates and pyrophosphates, such as pentasodium tripolyphosphate and tetrasodium pyrophosphate are preferred.

Trisodium nitrilotriacetate (NTA), preferably in the form of the monohydrate, and other nitrilotriacetates, such as disodium nitrilotriacetate, are preferred organic detergent salts. Sodium tripolyphosphate, sodium pyrophosphate and NTA can be used in hydrated or anhydrous form. Other water-soluble detergent salts which are considered to be effective are various other inorganic and organic phosphates, borates such as borax, citrates, gluconates, EDTA and iminodiacetates. Preferably the various water-soluble detergent salts should be in the form of alkali metal salts, either the sodium or potassium salts, or a mixture thereof, but usually the sodium salts are the more preferred. The silicates, preferably sodium silicates with a Nazi ratio in the range 1: 1.6, to 1: 3.0, preferably 1: 2 to 1: 2.8, eg 1: 2.35 or 1: 2.4, also serve also as water-soluble detergent salts, but due to their strong bonding properties they are suitably used to aid in agglomeration. The content of silicate in the product should generally not exceed 10 or 15%, with a content of 5 to 15% being suitable, preferably 3 to 7 or 8% when zeolite is not present and 0 to 2 or 5% in the presence of zeolite. (using only small amounts of silicate as a binder to retain the bentonite on the detergent or on the base grains of detergent when zeolite is present). In some cases, it may be desirable to subsequently add free-flowing sodium silicate, such as hydrated sodium silicate particles. In addition to the water-soluble detergent salts, water-insoluble detergent salts, such as zeolites, in particular zeolite A, preferably hydrated and containing, for example, 20% water, can be substituted for them, preferably only partially.

The bentonite used is a colloidal clay (aluminum silicate) containing montmorillonite. The type of bentonite clay most suitable in the preparation of the base grains of the invention is that known as sodium bentonite (or Wyoming or Western bentonite), and which usually consists of a light to off-white or brownish impermeable powder as in water. forms a colloidal suspension with strongly thixotropic properties. In water, the swelling capacity of this clay should usually be in the range of 3 to 15 or 20 ml / gram, preferably 7 to 15 ml / gram, and the viscosity at a concentration in water of 6% should usually be in the range of 3 to 30 centipois, preferably 8 to 30 centipois. The preferred bulging bentonites of this type are sold under the Mineral Colloid brand, such as industrial bentonites, by Benton Clay Company, a subsidiary of Georgia Kaolin Co. These materials, which are the same as those previously sold under the THIXO-JEL brand, consist of a selectively recovered and enriched bentonite, and those considered most suitable can be obtained in the form of Mineral Collid No's. 101 etc, corresponding to THIXO-JELs No's. 1, 2, 3 and 4. The pH values of the materials (6% concentration in water) are in the range 8 to 9.4, the maximum free moisture content is about 8% and the specific gravity about 2.6, and regarding the degree of pulverization so passes about 85% through the 200 mesh screen according to the American screen series. Enriched Wyoming bentonite is preferred as a component of the compositions of the invention, but other betnonites, including the synthetic bentonites (those made from exchangeable calcium and / or magnesium bentonites by treatment with sodium carbonate) are also useful. Likewise, the particle size can be reduced so that all bentonite passes through a No. 325 term. Although it is desirable to limit the maximum content of free water, as mentioned, it is even more important to make sure that the bentonite used has a sufficient amount of free water, most of which is considered to occur between adjacent bentonite slabs, for to facilitate a rapid decomposition of the bentonite and any other materials present in the particles, when the particles or detergent compositions containing them are brought into contact with water, such as wash water. It has been found that at least about 2%, at least about 3%, and preferably about 4% water or more should initially be present in the bentonite before it is mixed with the other grain components in the mixer, and this content should also be »» 25 30 35 466 '263 are present after spray drying or other drying procedure has taken place. In other words, excessive drying to the point where the bentonite loses its "internal" moisture can markedly reduce the usefulness of the compositions of the invention. When the water content of the bentonite is too low, the bentonite does not contribute to a satisfactory degree to the dissolution of the grains in the washing water. When the bentonite has a satisfactory water content, it may have a percentage of exchangeable calcium oxide of about 1 to 1.8%, and with respect to magnesium oxide this percentage may be between 0.04 and 0.41%. Typical chemical analyzes for these materials are from 64.8 to 73.0% SiO 2, 14 to 18% Al 2 O 3, 1.6 to 2.7% nga, 1.3 to 3.1 cao, 2.3 to 3.4% Fe, 0.8, 0.8 to 2.8% Nazu and 0.4 to 7.0% K, O. While some adjuvants, such as fluorescent whitening agents, pigments, such as ultramarine blue, titanium dioxide, polyacrylate, and inorganic salts in the form of fillers, may be added to the mixer, others, such as perfumes, enzymes, bleaches, certain dyes, bactericides, fungicides. and flow-improving agents, often sprayed on or otherwise mixed with the base granules or the spray-dried detergent compositions, any nonionic surfactant being added afterwards, and / or separately, so that they are not adversely affected by the elevated temperatures during spray drying, and in addition so that the presence of these in the spray-dried grains does not inhibit the absorption of nonionic surfactant when it is to be subsequently sprayed on the grains. In the case of stable and normally solid adjuvants, it is also often possible in the mixer to mix these with the initial mixture. In addition, any less stable adjuvants can be added to the agglomerate afterwards.

Of course, water is present in the mixer to serve as a dispersing medium for the various other components of the grains, and some water is present both in free form and in hydrated form in the product. When drying the grains, the moisture content, which should initially be between about 25 and 60%, can be reduced to about 5-15%, the moisture content being sufficient for the bentonite in the dried grains (in which it usually constitutes less than 10% and preferably does not occur) should contain at least 2% and preferably at least 4% water. Preferably, deionized water is used so that the content of hard ions therein can be very low, and so that the amount of metal ions which can promote the decomposition of any organic materials which may be present in the starting mixture or subsequently added materials is reduced to a minimum, but city water or tap water can usually be used instead. Normally the hardness of the water should be less than about 300 ppm, in the form of CaCO 3, preferably less than 150 ppm.

The levels of the various components in the base grains and in the grains of spray-dried detergent composition should be such as to obtain an effective cleaning agent with acceptable buoyancy, bulk volume and appearance. In most cases it should preferably be white, except that grains coated with betonite often appears darker in color (discolored) on closer inspection. If desired, a whitening agent may be used, such as TiO 2, in an amount of between 0.2 and 5% of the bentonite. However, it is also within the scope of the invention to add a coloring dye or pigment to the starting mixture so that the spray-dried grains (or otherwise produced grains) are colored.

It has been found that satisfactory grains of detergent compositions can be prepared which contain 2 or 5 to 30 or 35%, preferably 5 or 15 to 25 or 30%, for example 6 to 15% or 20 to 25% synthetic organic surfactant, and preferably anionic surfactant, 20 or 30 to 90%, preferably 30 or 35 to 80% 15 20 25 30 35 4ee'26s 11 or 85% and more preferably 35 or 45 to 70% detergent salt, 0.2 or 0 , 5 to 35 or 40%, preferably 0.5 or 1 to 20 or 30% and more preferably 1 to 10% or 1 to 20% adjuvant (s) and 3 to 20%, preferably 4 to 15% and still preferably 5 to 12% water, eg 7 or 8%. The grains, which can be produced by ordinary spray drying or by some other "equivalent" way, should usually have a spherical or other characteristic shape usually obtained by spray drying, and they often form perfect cores on which bentonite powder can be agglomerated.

They should generally have a bulk volume in the range of 0.2 to 0.7 g / cm 3, such as 0.3 to 0.5, eg 0.35 g / cm 3 '. The particle size is usually in the range of 8 to 100, and particles outside this range can be removed by sieving or some other separation procedure. Even better, the grain size should be between No. 8 or 10 to 40 or 60 according to the American screen series, and the grains are white or of some other color, which could be adversely affected by the application of commercially available brownish or discolored bentonite particles to the surface thereof, even if a dye is used together therewith in an attempt to mimic the original grain color. When the bentonite grains applied to the surface thereof are to be used directly, without mixing with detergent grains, they should preferably be white, not gray or brown, although a whitening agent such as TiO 2 must be used.

It has been found that when 10 to 60% by weight of the particles of the detergent composition have finely divided betonite powder agglomerated on the surface thereof and 90 to 40% by weight of the particles of the detergent composition lack such powder on the surface, the human eye does not notice the darker color. of the betonite-coated grains and does not detect any unpleasant brittleness of the product, at least not compared with products of similar composition in which the bentonite powder is evenly distributed over the spray-dried grains, or 466 263 10 15 20 25 30 35 12 in which only bentonite agglomerates are included, and the products according to the invention have thus not been found by consumers to be repulsively discolored. Preferred levels of the bentonite-coated material are 20 to 50% and 30 to 45%, eg 40%, the remainder being uncoated particles of the detergent composition. The amount of bentonite on the surface of the coated detergent granules is generally in the range of 10 or 20 to 80% by weight, preferably 35 to 65% by weight and more preferably 40 to 60% by weight, eg 50% by weight for the product to be used. mixed with betonite-free detergent particles. For the agglomerated particles to be used directly (without mixing with detergent particles) the range is 10 to 30% by weight, preferably 15 to 25% by weight, eg 20% by weight of the product. It has been found that since the spray dried grains are not massive, the application of these comparatively large quantities of bentonite does not dramatically change the particle size, although some increase may occur, such as about 5 to 15 or 30% of the grain diameter. The relatively small increase in the dimensions of the grains does not cause any separation or "flow" problems, and the presence of bentonite on the outside of the grains seems to help prevent separation of particles of different sizes during storage (compared to similar non-stick grains with a smooth surface ). Nor does it cause any undesirable changes with respect to the bulk volume of the product.

The application of the bentonite to the grains of detergent product (which in some cases may consist of grains of inorganic detergent salt, such as when nonionic surfactant is to be added afterwards) can be done using standard agglomeration techniques and equipment, such as the mixer-agglomerator type. with rotating drum similar to the one shown in the drawing. A method which has been found to be particularly suitable is to mix the desired amounts of detergent granules and finely divided bentonite powder and, while stirring, spray water or preferably spray a dilute sodium silicate solution onto the moving surface of the mixture. The spraying can take place at room temperature and gradually enough to prevent any unwanted clumping of the mixture. stirring should be continued in a known manner until all bentonite powder is retained on the detergent granules, after which stirring can be stopped and the product sieved or otherwise sorted so that it is within the desired size range. The silicate solution used when the agglomerate is to be mixed with detergent particles should generally have a concentration of 0.05 to 10%, such as 0.2 to 6%, eg 1, 2 or 4%. Sufficient amount should be used so that when present on the grains it is between 0.01 and 2%, such as 0.02 to 0.2 or 0.4%. When these concentrations are used in the application, satisfactory agglomeration and coating are obtained using a suitable agglomeration equipment, such as an O'Brien agglomerator, or a conventional inclined drum provided with a spray nozzle, baffle plates, etc. The amount of water sprayed on the grains is also not excessive. about 1 to 10% of the weight of the grains, eg 2 to 5 5, which percentage is smaller when based on the final product. The resulting product is hard enough to withstand treatment, packing and storage without any undesired pulverization and loss of the bentonite layer. Nor is the silicate concentration so high that it inhibits the dispersion of the bentonite in the washing water when the product is used in washing processes. Although silicate is preferably included in the agglomerating spray liquid, useful products can be obtained using only water as agglomerating agent or using aqueous solutions of other binders, such as rubber, resins, surfactants (surfactants), but in the absence of such materials, the bentonite, which have bonding properties, generally sufficiently adherent to give coated particles with the desired physical stability, which are rapidly dispersed in the wash water. If desired, a dye can be added to the spray liquid used in the agglomeration to color the resulting particles. In general, the concentration of dye should be less than 1% of the liquid to be sprayed, eg 0.01 to 0.1% thereof.

By using the dye only for the bentonite-coated particles, the resulting detergent product acquires an attractive appearance, and the "emollient particles" become color-identified. If you want to produce a completely colored product (and blue is the preferred color), the base grains can also be colored. In particular, ultramarine blue pigment can be applied together with the other components of the spray-dried detergent composition, and Acilan blue or Polar Brilliant blue (dyes) can be sprayed on the surface of the agglomerated bentonite particles.

In another embodiment of the present invention, the flowability of the resulting product can be improved by incorporating some or all of the most tacky components of the final product into the grains to be coated with bentonite. These grains are then coated with a protective film of agglomerated-finely divided bentonite particles and the tacky component is kept hidden under the bentonite layer and thus can not reduce the free-flowing properties. The other particles in the detergent, which do not contain any such component, become more free-flowing than would be the case if it were also included in their composition.

In addition, the tacky material can have a favorable effect on the agglomeration of the bentonite and the safe retention thereof on the surface of the base particles. In another embodiment of the invention, in fact, some or all of the synthetic organic surfactant, either in the form of an aqueous solution of anionic surfactant or as a nonionic surfactant in liquid form, is sprayed onto the base particles of the detergent composition before being mixed with the bentonite.

This surfactant spraying, rather than incorporating the same (or a portion thereof) into the mixture and spray drying it, improves the spray drying step and increases the throughput rate of the spray tower. In cases where the flow properties are not a problem and when a relatively large amount of nonionic surfactant is to be subsequently sprayed on the base grains of the detergent composition, it is of course not necessary or desirable that all surfactant or more than a proportional portion thereof be applied to the bentonite coated grains. is unsatisfactory, this embodiment of the invention provides a way to significantly improve it. When at least a part of the synthetic organic surfactant is to be spray-dried in the base grains, in general the grains to be coated with betonite must contain at least 10%, preferably 25% and more preferably 50% more surfactant than the other grains.

After preparation of the bentonite-coated grains, these can be mixed with materials to be added afterwards, or these materials can be sprayed on the surface of the grains, but generally the bentonite-coated grains are first mixed with the remaining spray-dried detergent material, after which any materials to be added after hand can be applied to or mixed with these. Such materials include enzyme powders, bleaches and perfumes.

Alternatively, some of these materials may be applied to or mixed with the various grains or applied to or mixed with some of these before the bentonite coated grains and the other grains are mixed together. It is also possible to add some of the adjuvants to the detergent grains afterwards before the application of bentonite to these grains, but this method is not generally applied. After mixing the various components in the compositions in question, these can be stored for a curing period of, for example, 1 to 24 hours, but usually no such curing is required but they can then be mixed with any adjuvants, if this has not been done. earlier. Thereafter, they can be transported to a packaging device for packaging, placed in cartons, stored and / or distributed.

The products according to the invention can, as previously described, when the detergent grains are white have a much whiter appearance than the corresponding products in which the bentonite to be applied is evenly distributed over all particles. This phenomenon seems to be due to the proportions between the grains and to some extent to the particle size of the grains. It is also important that the products according to the invention do not appear speckled despite the fact that they contain white and brownish particles. Nevertheless, they appear homogeneous and are light in color. When smaller levels of the concrete-coated particles are used than what is stated as the lower limit for the widest range specified here so that the darker color of these particles will not be repellent, the bentonite content of the product is usually lower than desirable. When a higher content of bentonite-coated particles is used than what is stated as the upper limit for the widest range specified here, the product becomes noticeably darker and discolored, and its appearance does not appeal to the average consumer, which makes the product difficult to market. . Specific differences between the reflection factors are not given here due to the varying nature of the commercially available natural and synthetic bentonites and their different color tones, but differences can be noted by means of a reflectometer, such as a Hunter reflectometer, or with a spectrophotometer, as such from General Electric Company. Usually, however, it is not necessary to use instruments to detect the color differences, as these can be so clearly distinguished by the average consumer. When different percentages of surfactant are present in the bentonite-coated and non-bentonite-coated grains and when the surfactant is applied to the grains to be coated with bentonite, improvements in the flowability of the product have been noted, as previously mentioned, and the resulting products appear to be considerably less sticky when touched and have less tendency to clump in the carton during storage. These improved properties can be verified by the standard tests used in the detergent industry, such as moving time, friction angle and packing tests.

It is thus clear that the properties of the final detergent products are improved without the need for adjuvants to improve the color, flowability or non-stickiness. Thus, the costs of these adjuvants and their other, sometimes undesirable properties are avoided.

Since only a part of the detergent granules is subjected to agglomeration, the throughput times in the agglomeration equipment are reduced. Advantages regarding both the composition and the process are thus obtained, and the final product is surprisingly improved compared to a product containing the same total quantity of bentonite applied to all particles in the detergent composition.

The following examples illustrate, but do not limit, the invention described in detail above. Unless otherwise stated, all parts are by weight and temperatures are by ° C. 466 10 15 20 25 30 35 263 18 EX§mQ§l_l BIQQQEL Linear sodium tridecylbenzenesulfonate 12 Pentasodium tripolyphosphate, hydrated 34 Sodium silicate (Na, 0: Si0, = 1: 2, 4) 7 Sodium sulfate 12 Borax 2 Sodium carboxymethylite cellulose 0.5 101, 200 mesh 20 [mesh size 0.074 mm], 7% water) Perfume 0.5 Water 12.0 100, 0 A detergent composition having the above composition was prepared by spray-drying a mixture of the components of the composition, with the exception of bentonite and perfume. (and with a slightly smaller amount of silicate to enable subsequent addition), at a moisture content in the starting mixture of about 35%, in a conventional commercial countercurrent spray drying tower under normal conditions and with a temperature of the drying air in the range 200-400 ° C, for the production of spherical grains of normal particle size in the range of No's 10 to 100 according to the American screen series. A portion of these grains were transferred to a O'Brien agglomerator or similar agglomerator and mixed there with the same weight of bentonite and with continued stirring the moving particle surfaces were sprayed with an aqueous solution (at room temperature) containing 5% sodium silicate, the total The amount of spray liquid applied was about 0.04 parts. The agglomeration was allowed to proceed for about 20 minutes, during which time the water evaporated, and thereafter essentially all the particles had a size within the sieve range 8 to 100 (mesh size 2.38 mm - 0.149 mm). Particles outside this range were removed and spray-dried detergent grains without bentonite coating in a quantity of 1.5 times which of the remaining coated particles (without added water) were then mixed with the bento rivet-coated grains in a tumbling drum for a period of 20 minutes, after which the product is perfumed and packaged in cartons. The spray-dried detergent prepared here had a moisture content of about 8 to 10%, but this can be changed by using barley and bentonite with other moisture contents and adjusting the spray liquid accordingly. Compared to a control product, prepared in the same way but with all detergent particles coated with bentonite (with the same total content of bentonite as in the final product according to the invention), the produced product had a lighter color, more even appearance (not "stained") and was more appealing to the human eye, which made it more acceptable to the consumer. If you want to produce a colored product, 2.0% ultramarine blue pigment can be included in the spray-dried grains, with 0.004% Acilan blue being included in the bentonite agglomerate for color matching. When silicate is excluded from the spray liquid during agglomeration, a satisfactory product can also be obtained, but after aging of such a product it becomes considerably more crumbly.

When the procedure described above is changed by mixing 0.3 parts of enzyme powder (Alcalase, 2 Anton units per gram) in the form of beads or powder (beads in the range of 10-100 mesh [mesh size 0.149 mm] and powder passing 200 mesh [ mesh size 0.074 mm]) before perfuming, the product still has a markedly improved appearance.

The various products according to this example are all satisfactory fabric softening finely divided detergents, usable in automatic washing machines for cleaning heavily soiled laundry. 466 265 10 15 20 25 30 35 20 EäšmQšL_¿ A product having the composition of Example 1 was prepared by spray drying two different compositions, one containing 24% linear sodium tridecylbenzenesulfonate and the other containing 12% thereof. The difference was offset by a decrease or increase in the sodium sulfate content of the respective compositions. The product having a higher content of anionic surfactant (and a lower content of sulphate) felt more sticky, and it was this product which was coated with the same amount by weight of bentonite powder (which passed through a No. 325 sieve [mesh size 0.044 mm]) and which was then mixed with non-bentonite-coated grains with a lower content of anionic surfactant in an amount of 1.5 times the weight of the agglomerate produced (which was agglomerated in the same manner as in Example 1). The mixture was then perfumed in the usual manner.

The resulting product had an improved flowability compared to the product of Example 1, probably due to the "insulating" effect of the bentonite particles agglomerated on the surface of the grains with higher content of anionic surfactant. Due to the stickiness of these grains, the amount of silicate solution applied could be reduced, in some cases to half of what was used in Example 1. In addition to obtaining a product which is more free-flowing, less sticky and less prone to baking during storage than the products according to Example 1 (which products are commercially acceptable), the presence of the higher content of anionic surfactant in the betonite-containing grains results in a faster decomposition and dispersion of the grains in the washing water, which improvement is benefited by the presence of a smaller amount of silicate in the bentonite coating. In some cases, as in Example 1, the silicate may be excluded from the agglomeration spray liquid, or the same amounts of other binders, such as sodium polyacrylate, polyvinylpyrrolidone or hydroxypropylmethylcellulose may be used instead. A further advantage of the method according to this example is that the amount of fine bentonite particles, which sometimes occur together with the bentonite agglomerate, is reduced, which is partly due to the sticky detergent. Example The procedure of Example 1 was varied by reducing the content of anionic surfactant in the spray dried granules from 15% to 14%, spraying the remaining anionic surfactant on the surface of the part of the granules to be coated with bentonite particles, via the agglomerating spray liquid. The sprayed material had a solids concentration of about 10% in water, and if the product produced became too tacky, heat and an air stream could be applied to reduce the moisture content and reduce the tack to an acceptable "tack" level. The detergent composition obtained after mixing the bentonite-coated grains with non-bentonite-coated grains was comparable to that of Example 2.

EXAMPLE When the linear sodium tridecylbenzenesulfonate of Example 1 was replaced with sodium hydrated tallow alcohol polyethoxy (3 EtO) sulfate, sodium hydrogenated tallow alcohol sulfate, sodium paraffin sulfonate or sodium olefin sulfonate paraffinate, the carbonate or to any two-component mixture thereof (of equal parts), products having properties comparable to those of Example 1 were obtained. This was also the case when the whole amount of pentasodium tripolyphosphate and sodium sulphate was exchanged for pentasodium tripolyphosphate, sodium carbonate, sodium bicarbonate mixture of zeolite A zeolite of equal parts thereof. Even when the amount of bentonite applied to the bentonite coated grains was changed to 15 and 25%, acceptable products with improved appearance were obtained, and this was also the case when the amount of bentonite coated particles was changed to 15 and 25%, respectively.

ExQMLeJJ Percent Sodium carbonate 22 Sodium bicarbonate 16 Zeolite A, hydrated (20% water) 32 Fluorescent bleach (Tinopal). 1.5 Water 9.0 Perfume 0.5 Nonionic surfactant (Neodol 23-6.5) ___l2____ 100.00 Detergent granules of the above composition were prepared by spray-drying a starting mixture containing 60% solids into granules of the specified particle size and containing all the mentioned ingredients, with the exception of perfume and nonionic surfactant, which were subsequently sprayed on the surface of the moving grains (although the perfume is preferably applied to the bentonite-coated grains after agglomeration). Due to the content of zeolite A, the nonionic surfactant was absorbed satisfactorily. A portion of this composition was then surface-agglomerated with a portion of bentonite powder (-325 mesh [mesh size 0.044 mm]), which appeared brownish after coating the particles.

After agglomeration is complete, 1-1 / 2 parts of non-bentonite coated grains of the detergent composition are mixed with the bentonite coated product. The final product was an excellent emollient detergent of the strong-acting, nonionic, detergent-activated detergent type and it had a whiter appearance than a control sample in which the bentonite was surface agglomerated on all the particles (with the same total content of bentonite). The product was a satisfactorily potent detergent.

According to a modification of the invention, a small amount, 0.1%, of blue dye (Acilan blue) in the silicate solution was sprayed on the surface of the particles in the agglomerator to color the particles.

When the production method was varied by spraying a larger amount of nonionic surfactant, eg 1/10 to 1/4 more surfactant, on the grains to be coated with bentonite than on the grains which were not to be coated, the flowability improved and the product produced was less sticky. .

The above description relates primarily to the object of the present invention which relates to the manufacture of a fabric softening detergent product having improved color (appearance) and flowability. The preparation of a detergent composition in which the bentonite agglomerates on the detergent particles will now be described in more detail. The resulting composition can, of course, be mixed with particles of the detergent composition or used without any such mixing.

Fig. 1 shows an open, inclined, cylindrical, rotating drum 11, which rotates about an axis with a relatively small acute angle in relation to the horizontal plane, the rotation taking place in the direction shown by the arrows 13 and 15. The drum 11 rests on rollers 17 , 19 and 21, which rotate in the opposite direction to the drum (counterclockwise, rather than clockwise as seen from the left), causing it to rotate as mentioned. The rotating drum 11 contains a mixture 23 of spray-dried detergent synthetic organic detergent grains and bentonite powder, which is agglomerated in the drum into fabric softening grains or particles of the detergent composition by spraying dilute sodium silicate solution 466 265 10 15 particles 24 while the mixture is in motion. Finished agglomerated emollient detergent particles 25 are removed from the drum 11 via the hatch 27. Spray nozzles 29, 31 and 33 are used to produce substantially conical jets of silicate solution, such as those designated No. 35, which penetrate into the movable the mixture of detergent grains and bentonite powder and promotes the agglomeration of the powder on the surface of the grains, although in some cases agglomerates may also be formed of bentonite alone or only detergent grains (the latter being less common).

In the rotating drum, the right or upper third or similar part is a mixing zone in which the bentonite and detergent grains are mixed in the dry state, the middle part is a spraying and agglomeration zone, and the lower third, or the like, is a zone where no spraying takes place. without the moistened particles and the agglomerate is "finished" to a relatively free-flowing product and as a result an agglomerate with the desired shape and character is obtained.

The above description relates mainly to a rotating drum, and this is a preferred embodiment of the apparatus used in carrying out the method according to the invention, although other similar devices may also be used. In addition to the rotating drum, there are also feeding devices for supplying the various components in the final product. Thus, the storage tank 37 contains sodium silicate solution 39 (which differs from the spray liquid 35), which is transferred to the spray nozzles 29, 31 and 33 via the line 41. The funnel-shaped container 43 contains detergent granules 45 which are transferred to the funnel 47 via a conveyor belt 49. Similarly, it contains funnel-shaped container 51 bentonite powder 53, which is transferred to the funnel 47 via the conveyor belt 55. Arrows 57 and 59 show the direction of movement of the respective belts. Fig. 2 shows how the mixture 23 in the drum 11 is lifted up against the left wall of the drum, which rotates in the direction of the arrow 13. When the mixture 23 falls downwards along the surface 61 of the upper wall, spray liquid 35, consisting of an aqueous solution of silicate, which is sprayed out in the form of a cone from the nozzle 29 and the other hidden nozzles 31 and 33, enters the movable mixture, moistening the surface of the core particles of detergent composition and facilitates the agglomeration of the bentonite on the grains, the more finely divided bentonite powder usually adhering to the surface of the larger particles of detergent composition. Constantly renewed surfaces or curtains of falling particles are brought into contact with the spray liquid, and a substantially even wetting of and application of silicate to the particles is obtained, which results in a smoother and better agglomerated product.

The particles of detergent composition, bentonite, silicate, adjuvants, etc. used in the agglomeration process as above are the same as previously mentioned in this specification.

When the agglomerated detergent particles, with the surface coated with bentonite, are to be used directly, a silicate solution which binds the bentonite to the detergent particles is preferably used. Although solutions with the concentrations and concentrations mentioned above can usually be used, the concentration of the silicate solution should be 2 to 8%, preferably 3 to 7% and more preferably 3 to 6%, eg 4 and 5%. Sufficient amount should be used so that the silicate from the spray liquid on the grains on which it is present constitutes between 0.1 and 0.4%, preferably 0.2 to 0.3% of the final product. At these application concentrations and amounts, a satisfactory agglomeration and coating is achieved using the rotating drum or other suitable agglomeration device. The amount of water sprayed on the grains is also not excessively large, usually about 3 to 6% by weight of the product. Deviations can be made with regard to the amount of water added by making the detergent granules correspondingly drier.

As with the previously described products, the resulting product is hard enough to handle handling, packing and storage without undesired pulverization and loss of bentonite coating. Furthermore, the silicate concentration is not so high that it counteracts the dispersion of the bentonite in the washing water when the product is used in washing processes. If desired, a dye can be added to the spray liquid used in the agglomeration to color the resulting particles.

Generally, the dye concentration should be less than 1% of the spray liquid, eg 0.01 to 0.1% thereof.

After the production of the concrete grains coated, these can be mixed with materials to be added afterwards or such materials can be sprayed on the surfaces of the grains.

Such materials are enzyme powders, bleaches and perfumes.

Alternatively, some of the mentioned materials may be applied to or mixed with the base grains or bentonite prior to agglomeration. After complete agglomeration, the products can be stored for a curing period of, for example, 1 to 24 hours, but usually there is no need for such curing, but the agglomerate can be mixed directly with any adjuvants if these have not been added before. The agglomerated grains are good detergents with marked emollient properties. In addition, they are free-flowing, non-dusting and mainly not easily crumble and they have good grain strength and abrasion resistance.

The following examples further illustrate the invention. In the mixer a slurry of 1009 parts of water, 2584 parts of detergent base (about 37% active ingredient and about 20% sodium sulphate, and the remainder of water), 841 parts of sodium silicate (Na; D: Si0, = 1: 2.4), 1315 parts of pentasodium tripolyphosphate, 542 parts of calcined soda, 24 parts of sodium sulphate and 293 parts of an aqueous solution of fluorescent whitening agents, antifoulants, stabilizers and other minor components in dilute aqueous solution. The mixing was carried out in a commercial detergent mixer at a temperature of about 55 ° C for a period of about 10 minutes after the addition of all the components, the solids content of the mixture being set at about 58 ° C during the mixing. This mixture was then pumped to a countercurrent spray drying tower, where it was forced through eight 10/10 type nozzles at a temperature of 52 ° C and a pressure of about 24 kg / cm 2. The temperatures in the tower were: ïg = 410 ° C and lg = 120 ° C. The detergent grains produced had a moisture content of about 7% and the spray rate was about 9000 kg / h. The obtained grains were sieved to a size in the range of 10 to 60 according to the American sieve series (mesh size 2.00 - 0.25 mm). The grains were white and had a bulk volume of about 0.3 g / ml.

An equipment, substantially similar to that illustrated in Figures 1 and 2, was used to agglomerate finely divided bentonite on the surface of the described spray dried granules of detergent composition. To prepare the desired about 20% bentonite product, No. 325 (mesh size 0.044 mm) sieved bentonite powder (containing about 5% water) with the grains of detergent composition in the ratio of 76.4 parts of base grain to 19.2 parts of bentonite. 3.8 parts of a 5% sodium silicate solution (Na 2 O: SiO 2 = 1: 2.4) were sprayed on the drum mixture in the rotary drum agglomerator mixer using a spray rod with 466 263 10 15 20 25 30 35 28 six nozzles (three are shown in the drawing) at a distance of about 1/2 meter from each other. The spray pressure was about 5 kg / cm 2, which gave a spray mist in which the diameters of the individual droplets were in the range of about 0.1 to 0.5 mm (mean value). After about 8 minutes of total mixing in the rotating drum, which was inclined at an angle of about 7 ° and about the last third of the drum was free from spraying with silicate liquid, the product was removed continuously, after which it was perfumed with 0.2 parts of a suitable perfume and 0.4 parts of enzyme powder were mixed therewith. In a variation of the process, the enzyme may be mixed with the product in the tumbling drum, in the last third thereof, with or without perfume.

The resulting product was a particularly suitable fabric softening atomized detergent which, if desired, could not see any layer within the range of Ne. io to sow or 8 to 100 (mesh size 2.00 to 0.25 mm and 2.38 to 0.149 mm, respectively, as desired. The bulk volume of the product was about 0.35 or 0.4 g / ml and it contained about 18% sodium dodecylbenzenesulfonate, 25% sodium polyphosphate, 9.5% sodium silicate, 9% calcined soda, 10% sodium sulfate, 19% bentonite, 0.4 % enzyme powder, 0.2% perfume, 0.1% fluorescent bleach and 9% water. The detergent granules were free-flowing, non-sticky, stable enough to be marketed, easily dispersible in the wash water and had an attractive appearance. In short, the product was an excellent fabric softener, strong-acting, disadvantageous detergent.

EK§mR§l_Z The procedure of Example 6 was followed except that the silicate solution applied contained 3% sodium silicate and the amount of solution applied was 4% of the total final product. The flowability, grain strength, non-crumb and abrasion resistance were satisfactory, as with the product of Example 6, and the product was a satisfactory, strong-acting, fabric-softening detergent composition. Even when the same amount of 6% sodium silicate solution was used, good results were obtained.

However, when the silicate solution had a concentration of 10%, the product became less satisfactory and contained lumps. When only water was used as the spray liquid, an agglomerate was obtained, but this tended to be of a higher degree of fineness and was generally less satisfactory than the agglomerates prepared using a sodium silicate solution having a concentration of 2 to 8%.

From these experiments and others in which the amount of silicate spray liquid has varied, it can be concluded that better products are obtained when the amount of spray liquid is about 2 to 8% (based on aqueous medium) of the product and the silicate deposited during the spraying is about 0 , 1 to 0.4% of the product.

EXšE2šl_§ The procedure of Example 6 was varied so that the calcined soda was excluded from the initial mixture and replaced with sodium sulfate. Likewise, the position of the spray nozzles in the rotating agglomeration drum can be changed, so that the bentonite and the grains of detergent composition 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 lower quarter. This resulting product was also a satisfactory fabric softening, finely divided, potent detergent, as well as those of Examples 6 and 7.

When a blue dye, such as Polar Brilliant blue, was present in a concentration of 0.2% in the silicate spray solution (or between 0.01 and 0.4%), colored products with attractive appearance were obtained. Ultramarine blue and other pigments may be used in place of or in combination with this dye.

Example fi Changes were made to the composition of the base mixture, the temperature, the mixing time and the mixing procedure and different conditions in the spray drying tower were used in the preparation of base grains of detergent composition. variations of i 10% and r 20% were made for the various components of the compositions of Examples 6-8, and also in the case of mixing times, nozzle pressures and other conditions (but these variations were kept within the ranges indicated), and good base grains were obtained which had a bulk volume of 0.3 to 0.5. The design of the nozzle, the pressure and the silicate concentration of the spray solutions, as previously described, also changed, and as long as the silicate concentration, the amount of silicate solution applied and the amount of silicate deposited with the bentonite on the base grain were within the previously given limits. This was also the case when the concentration of bentonite in the agglomerate end product varied in the range of 15 to 25%. Similar results can also be obtained when the detergent grains, agglomerated with bentonite, consist of nonionic detergent grains prepared by spraying nonionic surfactant in the liquid state on base grains of inorganic detergent salt, which grains are then agglomerated with bentonite and aqueous sodium silicate solution.

Good products were also obtained when, instead of using the very finely divided bentonite (through a No. 325 sieve [mesh size 0.044 mm]), such as THIXO-JEL No. 1 (Mineral Colloid No. 1,001) used in these examples used other bentonites, such as those made by the Amercan Colloid Company and those made from European and other bentonites containing exchangeable calcium and / or magnesium ions converted to sodium ions by treatment with sodium carbonate.

The invention has been described with reference to drawings and examples thereof, but it is not limited thereto since modifications and changes may, of course, be made without departing from the scope of the invention.

Claims (7)

'466 263 32 P a t e n t k r a v A process for preparing a fabric softening particulate, synthetic, organic detergent composition comprising bringing bentonite powder to adhere to the surfaces of the detergent composition particles, characterized by mixing a smaller amount of a finely divided bentonite powder with a larger amount of detergent. sprays the particle surfaces of the mixture while it is in motion so that new surfaces of the mixed materials are continuously exposed to the spray liquid, with a minor amount of an aqueous sodium silicate solution having a concentration in the range of 2 to 8% by weight in such a quantity. that the spray liquid deposits between about 0.1 and 0.4% by weight of sodium silicate and about 2 to 8% by weight of water on the mixture, exposes the mixture to continuous stirring after the addition of the aqueous sodium silicate solution and removes agglomerated particulate detergent with bentonite powder. retained on the surface thereof. 2. A method according to claim 1, characterized in that the bentonite powder, before the agglomeration, has such a particle size that substantially the entire amount thereof passes through a sieve with a mesh size of 0.074 mm, the size of the detergent particles, before the agglomeration, is in the range 0.149 to 2.38 mm, the bentonite constitutes between about 10 and 30% by weight of the fabric softening detergent composition produced, the sodium silicate having a Na 2 O: SiO 2 weight ratio in the range 1: 1.6 to 1: 3.2 and the concentration of sodium silicate in the aqueous spray liquid is in the range of 3 to 7% by weight. 3. A method according to claim 2, characterized in that the bentonite is a swelling bentonite, the detergent composition is a spray-dried, wash-activated, synthetic, organic detergent composition, the sodium silicate has a Na 2 Q: SiO 2 466 263 in 33 weight ratio in the range 1: 2 to 1: 3, the droplets in the aqueous sodium silicate spray liquid have an average diameter not exceeding 1 millimeter and the mixing, spraying, agglomeration and subsequent stirring take place continuously in a mixer of the rotary drum type. 4. A method according to claim 3, characterized in that the mixer of the rotating drum type in the longitudinal direction has a horizontal angle of between about 2 and 150, the initial mixing takes place within about the upper third of the length of the drum, the spraying takes place within about the middle third of the drum and the subsequent stirring takes place within about the lower third of the drum, the particles of the detergent composition and the bentonite powder being continuously introduced into the upper part of the drum, the spray liquid of sodium silicate solution being fed via a plurality of spray nozzles to the the agglomerated product has a bulk volume in the range 0.3 to 0.7 g / ml. A method according to claim 4, characterized in that the particles of spray-dried detergent composition comprise anionic synthetic organic surfactant and / or nonionic synthetic organic surfactant such as the active cleaning components, as well as sodium tripolyphosphate, sodium carbonate, sodium nitrilotrilotriacetate, sodium sodium , sodium citrate and / or sodium borate as detergent salts, the contents of which are in the range 5 to 35% and 30 to 90% respectively of the product. 6. A method according to claim 5, characterized in that the bentonite powder passes through a sieve with a mesh size of 0.074 mm, the spray-dried grains of the detergent composition have a particle size in the range 0.250 to 2.00 mm and comprise 15 to 30 weight % linear sodium dodecylbenzene sulfonate, 20 to 50% by weight of pentasodium tripolyphosphate, 5 to 15% by weight of sodium silicate with Na 2 O: SiO 2 weight ratio about 1: 2.4, 5 to 20% by weight of sodium carbonate, 5 to 30% by weight % sodium sulfate and 4 to 12% by weight of water, the sodium silicate spray liquid having a content of about 4 to 6% by weight of sodium silicate, the Na 2 O: SiO 2 weight ratio of the sodium silicate is about 1: 2.4, and about 3 to 6% by weight. % sodium silicate solution is applied to the mixture of detergent particles and bentonite. 7. A method according to claim 6, characterized in that the bentonite is a Wyoming bentonite having a water content of at least 4%, wherein the bentonite content of the fabric softening detergent composition is between 15 and 25% by weight thereof, the water content of the composition is between 7 and 15% by weight, the droplets of the spray liquid have an average diameter in the range between 0.1 and 0.5 millimeters, the agglomerated particles have a bulk volume in the range 0.3 to 0.5 g / ml, and the average residence time of the material in the rotating the drum is between 1 and 10 minutes.