NL8200805A - BASIC GRANULES AND DETERGENT COMPOSITIONS OBTAINED BY SPRAY DRYING. - Google Patents

Abstract

Free flowing spray dried beads which are useful as a detergent or for the manufacture of a particulate built synthetic nonionic organic detergent composition include water softening aluminosilicate (such as a zeolite), bentonite and water soluble builder, and may also include water soluble synthetic organic detergent and a small proportion of water soluble silicate, although such silicate is preferably omitted. The beads can be made to be of a bulk density within a broad range, and the bulk density may be varied by control of the bead formula and by modification of spray drying conditions. The base beads and detergent compositions formulated with them are of reduced aluminosilicate deposition characteristics, due to the presence of bentonite and the absence of or presence of only a low content of water soluble silicate, with the bead composition being maintained within given ranges. The moisture content of the beads will be such as to maintain at least 2% and preferably 3% or 4% or more of moisture in the bentonite so that its normal swelling power is retained, because the swelling of the bentonite is considered to be important in dispersing the beads in wash water and also, even more importantly, in helping to prevent aluminosilicate agglomeration and objectionable deposition thereof on materials washed, and in helping to break up any minor proportion of such agglomerates which might be formed.

Description

r VO 3122

Base granules and detergent compositions obtained by spray drying.

The present invention relates to free-flowing spray-dried base granules useful for the manufacture of a particulate synthetic nonionic organic detergent composition. The invention also relates to free-flowing detergent compositions obtained by spray drying. More particularly, the invention relates to such granules and compositions containing certain amounts (within prescribed ranges) of a water-softening aluminosilicate such as a zeolite, bentonite and a water-soluble detergent builder. The product obtained has a reduced tendency to zeolite deposition compared to known products containing similar amounts of the water-softening aluminosilicate. Such known products usually also contain significant amounts of a water-soluble silicate and usually do not contain bentonite.

In recent years, water-softening insoluble aluminosilicates, such as hydrated zeolites, have been used as a builder component and in laundry detergent compositions. Initially, a renewed interest in the zeolites appears to have been stimulated by the need to manufacture detergent compositions that do not contain phosphates. Trisodium nitrilotriacetate and other nitrilotriacetic acid (NTA) salts, which had been proposed as possible substitutes for phosphates, in particular pentasodium tripolyphosphate, which had been used in large quantities in the manufacture of laundry detergent compositions, were suspected here and there of a harmful and therefore compositions with ETA have not been marketed in the United States of America for years. There has never been any serious doubt that phosphates are safe for humans and recently the use of ETA has been disapproved. in detergents by the U.S. government withdrawn. Accordingly, detergent compositions containing phosphate and / or ETA may be placed back on the market, although certain detergent compositions will continue to be made without phosphate for use in areas near lakes and rivers where the phosphate tends to be a necessary provide nutrient soil for algae growth and thereby cause some eutrophication of such water.

Although the zeolites, preferably Zeolite A and most preferably hydrated Zeolite Ua, have been builder zoates in phosphate and NTA-5 free detergent compositions, it has now been found that they are also useful components for improved detergent and base granule compositions containing phosphate or phosphates and / or Contain MTA. Usually about 6 to 12% water-soluble sodium silicate has been used in crank mixes, from which spray-dried base grains or detergent compositions are made. The silicate has been used for its binding effect on the other components of the grain, which effect results in stable grains, and it has been found that said silicate helps to obtain a reticulated structure within the grain. It also acts as an anti-corrosion additive, which prevents chemical attack on aluminum-15 parts of washing machines and other appliances with which the detergent solution can come into contact. In the amounts previously used, e.g. 8-10% in the final product, however, it was noted that the combination of the water-soluble silicate and the zeolite in the crank mixer led to the formation of aggregates of such materials in the spray-dried granules, which aggregates undesirably deposited on the laundry, which can adversely affect the color appearance thereof. By the present invention, using certain amounts of zeolite, bentonite and water-soluble builder, with little or no water-soluble silicate, spray-dried granules of sufficient mechanical stability are obtained to be commercially acceptable and they have a reduced tendency to deposit zeolite (or a decreased tendency to deposit an aggregate of zeolite and silicate). Even when a small amount of silicate is present, the bentonite has been found to help counteract any tendency of the zeolite and the silicate to react to form a particle of a size larger than that of the normally present zeolite, thereby prevented or at least reduced the undesired deposition of zeolite or zeolite silicate particles on washed fabric. In addition, the compositions containing bentonite are much more easily disintegrated and distributed over the wash water, again apparently because of the presence of bentonite therein. Another advantage of the invention, when using little or no silicate, is that compositions containing carbonate and / or dicarbonate do not require the presence of gel-preventing materials to prevent excessive thickening of the crank mixture. Such additives are usually not necessary when the main builder of the detergent is a phosphate and when little or no carbonate and / or dicarbonate are present, but for phosphate-free compositions, which often contain significant amounts of carbonate and / or bicarbonate, the omission of gelling-preventing materials certainly is an advantage, both in processing and from an economic point of view.

The prior art regarding detergent compositions, softener compositions and detergent softener compositions includes the teaching that various detergent compositions can be prepared comprising one or more materials from the group consisting of zeolite, bentonite, silicate, phosphate, NTA , quaternary ammonium compounds (softeners), and other components, usually with a synthetic organic detergent, but although the publications contain comprehensive listings (sometimes referred to as "" laundry lists "") of virtually all materials that have been used for a variety of purposes in detergents and softener compositions, they do not contain a clear description or suggestion of the detergent compositions of the present invention, and this is especially true with respect to those compositions containing little or no soluble silicate. The publications do not appear to have recognized the importance of the bentonite containing sufficient "lubricating" water between the plates thereof, and apparently those publications have eluded the combination of binding and disintegrating effect, which can be attributed to the "hydrated" Bentonite Also, many of the reference regulations contain significant amounts of sodium sulfate, a filler, possibly to improve the physical properties of the product particles, but this is not necessary to prepare the present compositions, which thereby have a higher content of active ingredients (including builder).

According to the present invention, free-flowing spray-dried granules useful as detergents or for the manufacture of a particulate composite synthetic 8200805 <4 4 k organic detergent composition, which detergents have a lesser property of particulate deposition due to the presence of bentonite and a low content of water-soluble silicate or the absence of such a silicate in the granules obtained by spray-drying, calculated by weight, 5 to 6θ! water softening aluminosilicate, 2 to 10% bentonite, which contains enough moisture to facilitate dispersion of the bentonite, to prevent deposition of aluminosilicate on laundry, 5 to 60% of water-soluble builder or a mixture of such builders, 0 up to 30% water-soluble synthetic organic detergent and 0-5% water-soluble silicate. The aluminosilicate may be a zeolite with substantial calcium ion exchange capacity; the bentonite has a noticeable swelling capacity in water and contains a sufficient amount of moisture to facilitate the disintegration of its plate-to-plate bonds when the detergent granules are placed alone or mixed with other detergent component and in water; the water-soluble builder or water-soluble builder mixture is a polyphosphate, nitrile triacetate or carbonate; and no water-soluble silicate is present. Also within the scope of the invention are detergent compositions prepared by spray-drying the described grain prescription with an anionic detergent present in the crank mixture, or by spraying nonionic detergent in the liquid form on tumbling detergent-free granules or granules containing only relatively small amounts of an anionic detergent or a mixture of anionic detergents. Mixtures of such compositions, mixed anionic and nonionic detergent compositions, are also useful and may have better washing properties.

The zeolites used include crystalline, amorphous and mixed crystalline-amorphous zeolites of both natural and synthetic origin, which act sufficiently quickly and sufficiently effectively to block the calcium hardness causing ions in wash water. Preferably, such materials are able to react sufficiently quickly with the calcium ions so that, alone or together with other water softeners in the detergent, they soften the wash water before adverse reactions of such ions with other components of the synthetic organic detergent composition. Feature of the use- 8200805

♦ A

Zeolites are that they have a high exchange capacity for calcium ions, which is usually from about 200 to 400 or more mg equivalents of calcium carbonate hardness per gram of the aluminosilicate and preferably from 250 to 350 mg equivalent / g. They also preferably have a hardness-relieving efficacy from 0.02 to 0.05 mg of CaCO3 / l in 1 minute, preferably from 0.02 to 0.03 mg / 1, and less than 0.01 mg / 1 in 10 minutes, all this based on an anhydrous zeolite.

Although other ion exchange zeolites can also be used, the particulate synthetic zeolite builder particles used in the practice of this invention will usually correspond to the formula (Λ20) χ. (Al2O3) y. (Si0a) z 'v H 2 O where x has a value of 1, y has a value of 0.8 to 1.2, preferably of about 1.1, z has a value of 1.5 to 3.5, preferably from 2 to 3 or about 2, and w has a value from 0 to 9, preferably 2.5 to 6.

The zeolite should be a monovalent cation-exchanging zeolite, namely, an aluminosilicate with a monovalent cation, such as sodium, potassium, lithium (if usable) or another alkali metal, ammonium or hydrogen (sometimes). The monovalent cation of the molecular sieve formed by zeolite is preferably an alkali metal cation, especially sodium or potassium, most preferably sodium.

Crystalline types of zeolites useful as good ion exchangers according to the invention include, at least in part, zeolites having the following crystal structure groups: A, X, X, L, mordenite and erionite, of which types A, X and Y are the are preferred. Mixtures of such zeolites in the form of molecular sieves may also be useful, especially when the type A zeolite is present. These crystalline types of zeolites are well known in the art and are more particularly described in the book, "Zeolite Molecular Sieves", Donald W. Breek, published in 1977 by John Wiley & Sons. Typical commercially available zeolites of the above structural types are listed in Table 9.6 on pages 7-7-7-9 of the above-mentioned book. Such zeolites are known in the art. Some and others of such suitable 8200805 6 zeolites have been described in numerous patents in recent years for use as builders for. detergent compositions.

The zeolite used according to the invention is usually of a synthetic nature and is often characterized by a network of substantially equal pores in the range of about 0.3 to 1.0 nm, often of about 0.1 nm (normal ), said size being determined only by the unit structure of the zeolite crystal. Preferably, the zeolite belongs to type A or has a similar structure, in particular as described on page 131 of said book.

Good results have been obtained when a molecular zeolite sieve of the i + A type is used, wherein the monovalent cation of the zeolite is sodium and the pore size of the zeolite is about 0.1 nm and such zeolites are preferred ' from. Such molecular zeolite screens are described in U.S. Pat. No. 2,882.2 ^ 3, 15 which refers to those zeolites under the designation Zeolite A.

Molecular zeolite screens with ion exchange and water softening properties can be prepared in either dehydrated or calcined form, containing from about 0 or about 1.5% to about 3% moisture, or in a hydrated or water-containing form, 20 'which additionally bound water contains in an amount from about U to about 3% of the total weight of zeolite, depending on the type of zeolite used. The hydrated hydrated form of the zeolite molecular sieve (preferably hydrated to about 15 to 70% of its capacity) is preferred in the practical embodiment of this invention when a crystalline product is to be used.

The manufacture of such crystals is well known in the art. In the preparation of Zeolite A eg, as mentioned above, the hydrated zeolite crystals formed in the crystallization medium (such as an aqueous amorphous sodium aluminosilicate gel) are used without carrying out a high temperature dehydration (calcination to a water content of 3% or less), which is usually carried out in the preparation of such crystals for use as catalysts, e.g. cracking catalysts. The crystalline zeolite, in either fully hydrated or partially hydrated form, can be recovered by filtering the crystals from the crystallization medium and drying them in air at ordinary temperature, so that their water content is in the range of about 8200805 τ 5 to 30 $, preferably about 1¾ or 15 to 25%, such as 1? up to 22 $, for example 20 $. However, the moisture content of the type of molecular zeolite screen used may be lower, as previously described, in many cases the zeolite can be hydrated during mixing in the crank mixer and other treatment steps.

The zeolite is preferably in a finely divided state, the largest particle diameters being up to 20 µm, e.g., 0.005 or 0.01 to 20 µm, more preferably 0.01 to 15 µm, e.g. 3 to 12 µm, and most preferably 0.1 to 8 µm, average particle size, e.g. 3 to 7 µm, when crystalline, and 0.01 to 0.1 µm, e.g. 0.01 to 0.05 µm, if amorphous. Although the largest particle sizes are much smaller, the zeolite particles will usually have sizes in the range of a mesh size from 0.19 to 0.037 mm and preferably from 0.105 to 0.0 W mm. Small-sized zeolites are often undesirably dusty, and larger-sized ones may not adhere sufficiently and satisfactorily to carbonate, bicarbonate, phosphate and / or NTA base cores on which they can be distributed with the bentonite, such as in a gel-like or film state, during spray-drying of a crank mixture to form base grains.

The bentonite used is a colloxal clay (aluminum silicate) containing montmorillonite. Montmorillonite is a hydrated aluminum silicate, in which about 1 / 6th of the aluminum ions may have been replaced by magnesium ions and which can loosely combine varying amounts of hydrogen, sodium, potassium, calcium, magnesium and other metals. The type of bentonite clay most useful in making the subject base granules is the type known as sodium bentonite (or Wyoming or Western bentonite), which is usually a light to cream colored intangible powder, which is a collolda in water -le suspension with strong thixotropic properties. In water, the swelling capacity of the clay will usually be in the range from 3 to 15 cm / g, preferably from 7 to 15 cm / g, and its viscosity, at a concentration of 6% in water, will usually be ranging from 3 to 30 cP, and preferably from 8 to 30 cP. Preferred swelling bentonites of this type are commercially available under the name Mineral Colloid as industrial bentonites from Benton Clay Co., a subsidiary of Georgia Kaolin Co. These materials, which are the same as 8200805 8 those previously sold under the name Thixo-Jel, have been selectively quarried and improved bentonite, and those considered to be most useful are available as Mineral Colloid Nos. 101, etc. corresponding to Thixo-Jel Nos. 1, 2, 3 and 1+. Such materials have pH values (concentration of $ 6 in water) in the range of 8 to 9.1+, maximum free moisture levels of about $ 8, and specific gravities of about 2.6, and of the powdery quality passes about 85% through a sieve with a mesh size of 0.07 mm. Improved Wyoming bentonite is preferred as a component of the present compositions, but other bentonite species are also useful, especially when they are a minor part of the bentonite used. Although it is desirable to limit the maximum free moisture content, as stated, it is even more important to ensure that the bentonite to be used contains sufficient free moisture, the bulk of which is believed to be present between adjacent plates of the bentonite, to facilitate rapid disintegration of the bentonite and all adjacent materials in the particles when such particles or detergent compositions containing them are contacted with water, such as wash water. Sr has found that initially at least about 2%, preferably at least 3%, and most preferably about k% or more water should be present in the bentonite before mixing with the other grain components in the crank mixer (crutcher) , and such an amount should also be present after spray drying. In other words, drying beyond the point where the bentonite loses its "internal" moisture can significantly reduce the utility of the present compositions. When the moisture content of the bentonite is too low, the bentonite does not work to prevent formation of silica a-z eobetagglomerat and does not help disintegrating the granules in the wash water either. When the bentonite has sufficient moisture content, it exhibits an exchangeable calcium oxide percentage in the range of about 1 to 1.8 and with respect to magnesium oxide, that percentage is usually in the range of 0.0U to 0.1 + 1. Typical chemical analyzes of such materials indicate the following composition: 61+, 8 to 73.0, $ 35 SiO2, 1.1 + up to $ 1.8 Al203, 1.6 to $ 2.7 MgO, 1.3 to $ 3.1 CaO, 2.3 to 3.1 + $ Fe203, 0.8 to $ 2.8 MfO and 0 .1 + to 7.0 $ K20.

8200805 s * 9

The water-soluble builder used or use-. the mixture thereof may consist of one or more of the usual materials which have been used as builder or proposed for such purposes. These include inorganic and organic builders and mixing thereof. Among the inorganic builders, preference is given to the various phosphates, preferably polyphosphates, e.g. tripolyphosphate and pyrophosphates, such as pentasodium tripolyphosphate and tetrasodium pyrophosphate. Trisodium nitrilotriacetate (HTA), preferably used as the monohydrate, and other nitrilotriacetates, such as disodium nitrilotriacetate, are preferably used in more soluble builders. Sodium tripolyphosphate, sodium pyrophosphate and NTA can be used in hydrated form, but even when vessel-free compounds are used, it appears to prevent bentonite and zeolite cake formation during the next hydration. Of course, carbonates, such as sodium carbonate, are useful builders and can be used desirably, alone or in combination with bicarbonates, such as sodium bicarbonate. When the polyphosphates are used, it may be preferable to have sodium pyrophosphate present together with sodium tripolyphosphate in a ratio of 1:10 to 10: 1, preferably 1: 5 to 5: 1 over 20, including the total amount of both builders is about the same as that previously reported for the sodium tripolyphosphate. Other more soluble builders which are considered to be effective include the various other inorganic and organic phosphates, borates, e.g. borax, citrates, gluconates, EDTA and iminodiacetates. The various builders 25 will preferably be in the form of their alkali metal salts, either the sodium or potassium salt and, or a mixture thereof, but usually more preferred is sodium salts. In some instances, such as making neutral or slightly acidic detergent compositions, there may be preference for acidic forms of the builders, and especially of the organic builders, but usually the salts will be either neutral or basic in nature. The silicates, preferably sodium silicate, with a ratio ITagO: SiOg in the range from 1: 1.6 to 1: 3.0, preferably 1: 2 to 1: 2.8, e.g. 1: 2.35 or 1: 2th, also serve as builder salts, but due to their strong binding properties and their tendency to promote aggregate or agglomerate formation with zeolite particles, they are special cases of builders and it has 8200805 10 is preferred to omit them from the present compositions. However, since they have anti-corrosive properties, which is important when the detergent solution is to be used in washing machines or in other appliances in contact with aluminum parts thereof, they can sometimes still be present in limited small amounts. In such cases, it may be preferable to add hydrated sodium silicate particles afterwards so that they do not react or agglomerate with zeolite particles during mixing in the crank mixer and spray drying. Although sodium sulfate and sodium chloride as well as T0 other filler salts do not have builder properties, they are sometimes used in detergent compositions because of their filling properties. In addition to increasing the volume and weight of the product, thereby facilitating dosing, they also sometimes improve the grain stability and physical properties of the detergent composition granules in which they are applied, nevertheless, since the present compositions are satisfactory without whatever fillers are contained therein, such compositions are preferred in which no fillers are present at all or only a minimal amount thereof, usually a practical minimum.

Usually, the detergents used will or will normally be either nonionic or anionic or both, but there may also be amphoteric or ampholytic. detergents are used, especially in combination with nonionic and / or anionic detergents in the present compositions. Cationic detergents can serve as a fabric softener in these products, but will not usually be spray dried with anionic detergents, because of an undesired interaction which can then occur. These classes of materials are well known and have been repeatedly described in the detergent field. Since they are not preferred components of the present composition® 30, a further description thereof is not considered desirable in this context.

Although various non-ionic detergents with satisfactory physical properties can be used, including condensation products of ethylene oxide and propylene oxide and each other and with hydroxyl-containing bases, such as nonylphenol and oxo-type alcohols, very much preferred to a nonionic detergent 8200805 11 which is a condensation product of ethylene oxide and a higher fatty alcohol. In such products, the higher fatty alcohol has 10 to 20 carbon atoms, preferably 12 to 16 carbon atoms, and the nonionic detergent contains from about 3 to 20 or 30 ethylene oxide groups per mole, preferably from 6 to 12. Preferably the nonionic detergent is one in which the higher fatty alcohol has about 12 to 13 or 15 carbon atoms and contains from 6 to 7 or 11 moles of ethylene oxide. Such detergents are manufactured by Shell Chemical Co. and are available under the names Neodol 23-6.5 and 25.7. Their particularly attractive properties include, apart from the fact that they have a good detergency against oil stains on laundry, a fairly low melting point, but still significantly above room temperature so that they can be sprayed on base granules in the form of a liquid which solidifies.

Various anionic detergents can be used, usually as sodium salts, but the most preferred are linear higher alkyl benzene sulfonates, higher alkyl sulfates and higher fatty alcohol polyethoxylate sulfates. In the higher alkyl benzene sulfonate, the higher alkyl group is preferably linear with 12 to 15 carbon-20 atoms, e.g. 13, and that sulfate is preferably in the form of a sodium salt. The alkyl sulfate is preferably a higher fatty alkyl sulfate having 10 to 18 carbon atoms, preferably 12 to 16 carbon atoms, e.g. 12, and is also used as a sodium salt. The higher alkyl ethoxamer sulfates will analogously have 10 or 12 to 18 carbon atoms, e.g. 12, in the higher alkyl group, which is preferably a fatty alkyl group, and the ethoxy content will usually be from 3 to 30 ethoxy groups per mole, preferably 3 or 5 to 20. Here too, preference is given to the sodium salts. Thus, it is understood that the alkyl groups are preferably linear or are higher fatty alkyl groups having 10 to 18 carbon atoms, the cation is preferably sodium, and, when a polyethoxy chain is present, the sulfate is at the end thereof. Other useful anionic detergents are the higher olefin sulfonates and paraffin sulfonates, e.g. the sodium salts, the olefin or paraffin groups containing 10 to 18 carbon atoms. Specific examples of the preferred detergents are sodium tridecylbenzene sulfonate, sodium tallow alcohol polyethoxy (3 EtO) sulfate and sodium hydrogenated tallow alcohol sulfate. In addition to the aforementioned preferred anionic detergents, other detergents of this well-known group may also be present, especially in only small amounts from those previously described. Mixtures thereof can also be used and in some cases such mixtures may be better than separate detergents. The various anionic detergents are well known in the art and are described in detail on pages 25-138 of "Surface Active Agents and Detergents", Volume II, by Schwartz, Perry & Berch, published in 1958 by Interscience Publishers Inc.

Various additives may be present in the stool-10 mixture from which base granules or detergent compositions may be spray dried, or such additives may be added afterwards, the decision on the manner of addition often being determined by the physical properties of the additives, their heat resistance and against decomposition in the aqueous medium of the crutch mixture and by its volatility. More important additives include a polyacrylate, which has been found to be useful in controlling the grain characteristics and bulk density, which has dispersant, sag-inhibiting and redeposition-inhibiting effects in the present compositions, and helps keep the crank mixture fluid and 20 to keep it homogeneous.

The polyacrylate, which is present in preferred basic granules of this invention, is a low molecular weight polyacrylate, which usually ranges from about 1,000 to 5,000, preferably from 1,000 to 3,000, most preferably from 1,000 to 2,000, especially 25 example is approximately 2,000. The polyacrylate can be partially or completely neutralized, e.g. about 1/2 or 1/3 may be present as sodium polyacrylate. Although modified polyacrylates can be used in place of the disclosed sodium polyacrylate, including some other alkali metal polyacrylates and hydroxylated polyacrylates, it is preferable to limit such replacements to a minor amount of the material and the polyacrylate is preferably an unsubstituted sodium polyacrylate. Such materials are available from Alco Chemical Corporation under the name "Alcosperse". The sodium polyacrylates are available as clear ambe liquids or powders, the solutions having a solid content of about 25 to 10% 3 e.g. 30%, and the pH of such solutions or of a 30 # 's aqueous solution The powder is in the range of about 7.5 to 9.5, e.g. 9. Such materials are completely soluble in water and have been used as dispersants. They have been shown to be capable of binding calcium ions and have been used to prevent the deposition of insoluble calcium compounds from aqueous solutions. In the present spray drying process, small amounts (or percentages) thereof help to give the resulting granules a better porosity.

When the crank mixture contains carbonate and / or bicarbonate and silicate, even when the amount of the silicate is small, the mixture may tend to gel or solidify in the crank mixer, especially when due to processing delays the stool mixture is stored longer than the normal time of about 30 minutes. When such cases of silicate are present, it is preferred that also auxiliary auxiliary agents be present in the mixture (and consequently in the final base grains and detergent composition) in order to prevent premature solidification or gelling. Those processing aids most preferably include citric acid and magnesium sulfate. Soluble citrates, such as sodium citrate, may also be used in place of citric acid, and although it is preferred to use anhydrous magnesium sulfate, hydrates thereof such as epsom salts may also be used. Magnesium citrate can also be replaced. Instead of the preferred gel-preventing system, other means and suitable systems to keep the crank mixture fluid, such as sodium sesquicarbonate, may be used to replace part of the sodium carbonate and sodium bicarbonate. While such processing aids are useful in many instances, it is a feature of this invention that they are not necessary for the manufacture of the preferred base granules in which silicate has been omitted.

Although some additives, such as fluorescent brighteners, pigments, e.g. ultramarine blue, titanium dioxide and inorganic filler salts can be added in the crank mixer, others such as fragrances, enzymes, bleaches, some dyes, bactericides, fungicides, fabric softeners and liquid promoters often on the base granules or the spray dried detergent composition 8200805

Hlling are sprayed or otherwise mixed therewith along with any nonionic detergent and / or independently thereof so that they will not be adversely affected by the higher temperatures of the spray drying operation and also such that their presence 5 in the granules obtained by spray drying does not prevent absorption of non-ionic detergent when such detergent is sprayed onto the granules afterwards. However, stable and normally solid additives are also possible. be mixed with the starting slurry in the crank mixer. Thus, it is possible, when using pigments and fluorescent brighteners, that they are simply present in the crank mixture from which the subject base granules are sprayed. The preferred colorant is ultramarine blue, but other stable pigments and dyes can be used together with or as a substitute for it. Because the spray granules of the present invention obtained by spray drying may sometimes be tinted, usually due to the use of natural minerals, the tint from such a colorant may be adversely affected. It has been found that incorporating a small amount of titanium dioxide into the stool mixture helps to maintain the desired shade of the colorant and the presence of the titanium dioxide does not appear to have any adverse effect on the appearance of the laundry being washed with detergent compositions prepared from base granules containing titanium dioxide.

As a fluorescent brightening substance, 25 Tinopal 5BM is used, especially in highly concentrated form. However, various other cotton brighteners may also be used, such as those sometimes referred to as CC / DAS brighteners derived from the reaction product of cyanuric chloride and the disodium salt of diamino stilbene disulfonic acid, including modification products thereof with respect to substituents on the triazine and aromatic rings. This class of brighteners is known in the detergent art and will be used very often when no bleaching components are present in the final product. When the detergent composition is desired to contain a bleaching agent, such as sodium perborate or other oxidizing bleaching agent, bleaching stable brighteners will usually be included in the crank mixture. As such may be mentioned the benzidine sulfone disulphonic acids, naphthotriazolyl stilbene sulfonic acids and benzimidazolyl derivatives. Polyamide brighteners, which may also be present, are aminocumarin or diphenylpyrazoline derivatives, and polyester brighteners which may also be used are naphthotriazolyl stilbene. Such brighteners are usually used in the form of their soluble salts, but they can also be added as the corresponding acids. Cotton brighteners usually comprise fairly large amounts of the brightening systems used.

Enzyme preparations, which are usually retrofitted to the base granules because they are sensitive to heat, may be of any variety of commercially available products, including Alcalase, manufactured by Hovo Industri A / S, and Maxa-15 tase, both of which are alkaline proteases (subtilisin). Maxazyme 3T5 is sometimes preferred. Although the alkaline proteases are most often used, amylotic enzymes such as α-amylase can also be used. The said compositions usually contain active enzymes in combination with an inert powdery carrier, such as sodium or calcium sulfate, and the amount of active enzyme can vary within wide limits, but is usually from 2 to 80% of the commercial composition. When amounts are mentioned in this description, they refer to the enzyme preparations and not only to the active part thereof. Used fragrances, which are usually heat sensitive and may contain volatile components, including a solvent such as alcohol, normally consist of synthetic fragrance materials, sometimes mixed with natural components, and generally contain alcohols, aldehydes, terpenes, fixatives and other normal perfume components -nents. Flow promoters, such as special clays, which are sometimes added to detergent products, although often useful in improving flow and reducing tackiness of various compositions, are not necessary in the present case, possibly in part because of the presence of the bentonite and the absence or only very limited presence of silicate.

However, if desired, they can be added in order to further improve the flow behavior. Although it has been found that detergent compositions made from the present basic granules of 8200805 do not require the presence of any corrosion additives to replace the omitted silicate, it is within the invention to use suitable such substances and it has the preferable to use those which are stable under the conditions prevailing in the mixing in the crank mixer and spray drying and which do not adversely affect such treatments Such anti-corrosive additives or antioxidants may be organic or inorganic in nature, usually the inorganic materials are preferred, and they are preferably selected for their ability to resist corrosion of aluminum parts of washing machines When it is desirable to continue using a silicate for such purpose or to use a silicate because of its effect on the magnet hardness-induced hardness, is usually preferred is a powdered silicate, such as aqueous sodium silicate, which is commercially available under the name Britesil, manufactured by Philadelphia Quartz Co. (Wa ^ O: SiOj = 1: 2, b) and that agent is preferably added afterwards. However, other normally solid soluble silicates, preferably of alkali metals, may also be retrospectively added to the granules of this invention, preferably after any nonionic detergent absorption to be performed.

If it is desired that the manufactured product have fabric softening properties, softening materials, preferably in the form of a dry powder, may also be conveniently added to the base grains afterwards. This class of materials is well known and such softening agents are usually cationic compounds, especially quaternary ammonium compounds, such as quaternary aramonium halides. Particular preference is given to the higher alkyl, alkylaryl and arylalkyl-lower-alkyl quaternary ammonium chlorides and bromides, such as distearyl dimethyl ammonium chloride. Among the commercially available fabric softening materials, most preferred is the material sold under the name Ar osurf TA-100 manufactured by Sherex Chemical Co. Incorporated. Such compounds also have anti-static and anti-bacterial properties, but if desired other anti-bacterial additives may also be used, which are preferably also incorporated in the product by post addition.

Of course, water is present in the crank mixer to serve as a medium for dispersing the various other grain components, and a little water, both in free form and hydrate form, is present in the product. drying the granules may reduce their initial moisture content, which is about 25 to 60%, to about 5 to 15%, such moisture content being sufficient that the bentonite in the dried granules is at least 2%, and preferably at least k% moisture. It is preferable to use demineralized water, so that the degree of hardness thereof can be very low and so that metal ions, which decompose all kinds of organic materials, which may be present in the crank mixture, base grains and detergent, are minimized limited, but ordinary tap water can usually also be used instead.

Usually, the hardness of such water will be less than 150ppm, as CaCO2, and most preferably, its hardness will be less than 100ppm, and more preferably even less than 50ppm.

The amounts of the various components in the base grains and in. the spray-dried granules of the detergent composition will be free-flowing and, as far as the base granules are concerned, sufficiently absorbent for a nonionic detergent to be applied to them in a liquid state, so that the detergent compositions be free-flowing. The detergent compositions will, of course, also be effective detergents, the builders present acting to aid the organic detergent in its cleaning effect in aqueous solutions of the compositions; it is important that the products obtained are such that they do not cause unwanted deposits of zeolite particles (or zeolite silicate aggregates) on the crops. The zeolite particles and the bentonite particles, although insoluble, will not undesirably discolor or discolour the laundry due to their small particle size, but such discoloration can occur when zeolite aggregates are formed that are large enough to adhere to fabric and also for easy viewing through the eye, especially when substantial amounts thereof are not removed from the laundry by the drying air during automatic drying.

8200805 18

It is also desirable that the prepared base grains and grains of the detergent composition have a suitable bulk density and color.

It has been found that suitable granules for achieving the aforementioned objectives, by weight, are from 5 to 60% water softening aluminosilicate (zeolite), 2 to 10% bentonite (with the desired moisture content) and 5 to 60% water soluble builder or mixture of such builders. From 0 to 30% water-soluble synthetic organic detergent and / or from 0 to 5% water-soluble silicate may also be present, but are often preferred to be omitted. The granules obtained by spray-drying preferably contain from 3 to 50% moisture, more preferably from 5 to 12% and usually from 7 to 10%, including any hydrate water present. Such hydrate water may be present in the zeolite, ΕΡΓΑ, phosphate, carbonate, bicarbonate and magnesium sulfate, when present in the composition, in addition to the water contained between the plates of the bentonite. The said moisture content even includes strongly bound hydraafc water, such as the water still retained in the zeolite, even after several hours of distillation of a dispersion in toluene. In some cases, such as when the zeolite concentration in the product is high, so that up to about 12 - 1-5% moisture may be present as hydrate water in the zeolite, the moisture content in the spray-dried granules may be up to 20%. % and sometimes even up to about 25%. However, for good flowability of the product and to minimize sticking and clumping, that upper limit will normally be about 15%, especially when the final detergent composition contains a noticeable amount of a nonionic detergent. The said percentage of zeolite includes the hydrate water contained therein. It is possible to make useful spray-dried granules with a moisture content of less than 3%, provided that sufficient water is associated with the bentonite, for the reasons previously mentioned, but because of the strong moisture attraction of the zeolite and because of the action of other hydratable materials which may be present has been found that usually a minimum of 3% moisture is required to avoid loss of the desired internal moisture of the bentonite, which moisture appears to "lubricate" the plates and their separation appears to be facilitated 8200805 19 when a product containing those granules is dispersed in water. Also, when anhydrous products are manufactured, even if sufficient moisture is retained in the bentonite, it is true that they are sensitive to be physically unstable, easier to powder and 5 subject to abrasion and disintegration.

The bulk density of the spray drying obtained by spray drying may range from 0.2 to 0.9 g / cm. Bulk weights in the lower part of this range can be more easily obtained when no silicate is present in lift crank mixture that is spray-dried and when little or no non-ionic detergent is absorbed by the granules. The higher bulk densities are obtained when non-ionic detergent is applied to porous granules and when a little silicate is present in the granules. Such lighter products have bulk weights ranging from 0.2 to 0.5 O 3 g / cm, often from 0.3 to 0.4 g / cm, and the heavier particles have

O

bulk weights in the range of 0.6 to 0.9 g / cm, usually from 0.6 to 0.8 g / cm. The dimensions of the grain particles are usually in the range of sieves with mesh sizes from 2.00 to 0.149 mm and preferably from 2.00 to 0.250 mm. In preferred compositions, the ratio of bentonite to zeolite is in the range of 1: 4 to 1: 1, the ratio of water-soluble builder to zeolite is in the range of 1: 2 to 3: 1 and the ratio of bentonite to water-soluble builder in the range from 1:10 to 1: 1 ... Most preferably, the aforementioned ratios lie in the range of resp.

1: 3 to 2: 3, 2: 3 to 2: 1 and 1: 6 to, 1: 2. Percent values, the compositions preferably comprise from 10 to 40% 41 of a partially hydrated sodium zeolite, which is preferably of 15 to 25% by weight, containing hydrate water and having an exchange capacity for calcium ions in the range of 200 to 400 mg of 30 equivalents of calcium carbonate hardness per g of anhydrous zeolite, 2 to 35% bentonite, which is of a type with a swelling ability in the range of 7 to 15 cm / g and having a viscosity in the range of 8 to 30 cP at a concentration of 6% water, 10 to 50% of a water-soluble alkali metal builder salt or mixture thereof, 0 to 25 % of a water-soluble synthetic anionic organic detergent and 0 to 3% of a water-soluble silicate, which silicate, if present, is an alkali metal 8200805 20 • silicate with an alkali metal oxide: silica ratio in the range of 1: 1.6 to 1: 3, love t from 1: 2 to 1: 2.8. More preferably, granular compositions include $ 15 to $ 35 Zeolite, $ 5 to $ 20 enhanced Wyoming bentonite, $ 20 to $ 50 water-soluble sodium builder salt or 5 mixture thereof, $ 0 to $ 20 water-soluble synthetic anionic organic detergent, and $ 0 sodium silicate.

Although carbonate and bicarbonate builders are useful for making base granules of this invention, especially those onto which a nonionic detergent is sprayed, polyphosphate and / or nitrilotriacetate builders are preferred for spray drying. granules, whether or not they contain an anionic detergent and whether or not they are intended to contain a. non-ionic detergent. Preferred base grain compositions based on HTA 'as the sole or major soluble builder include from 15 to 35% or 40% hydrated zeolite, 5 or 10 to 20% bentonite and 20 to 50 or 60% HTA. When a phosphate, such as sodium tripolyphosphate, is the primary water-soluble builder or base builder ,. the same amounts of zeolite and bentonite can be used, but usually more phosphate may be present (than 20 HTA). For such base granules on which a non-ionic detergent is sprayed, or for similar carbonate-based compositions or a mixture of bicarbonate and carbonate (wherein the carbonate: bicarbonate ratio in the spray-dried base granule is in the range of about 1 to 3), preferably no water-soluble synthetic organic detergent and little or no water-soluble silicate will be present. When bicarbonate and carbonate are used together in such compositions, they will usually make up a total of 20 to 10% of the base grains, and when carbonate alone is used, it will usually make up 10 to 30% thereof.

When an anionic detergent or other suitable organic detergent is incorporated into the articulated mixer to produce a spray-dried detergent product, preferred amounts thereof will be from 3 to 5 to 30%, more preferably from 5 to 25% and preferably 10 to 25 $, eg 10 $, 15 $, of such a product, and the detergent will preferably be selected from the group consisting of sodium linear alkyl benzene sulfonate, wherein the alkyl group contains 10 to 18 carbon atoms, "sodium fatty alcohol sulfate, wherein the alcohol is from 10 to 18" carbon atoms ", and sodium fatty alcohol ethoxylate sulfate, wherein the fatty alcohol contains from 10 to 18 carbon atoms and contains from 3 to 30 ethylene-5 oxide groups per mole, and mixtures thereof. Presently, the most preferred detergents are sodium linear tri-decylbenzene sulfonate and the alkyl groups preferably contain 12 to 16 carbon atoms.

When a nonionic detergent is absorbed in tO the spray-dried base granules (and sometimes a small amount can be absorbed in the spray-dried detergent granules), the amount thereof will usually be in the range of 5 or 8 to 30%, preferably 10 to 25%, e.g. 15% * 20 $. In such cases, the preferred nonionic detergent 15 is a condensation product of 6 to 12 moles of ethylene oxide and 1 mole of a higher fatty alcohol of 12 to 16 carbon atoms.

When polyacrylate is present in any of the detergent compositions or base granules, it will usually be from 0.05 to Λ% thereof, and its molecular weight is preferably in the range of 1,000 to 5,000.

Since the presence of an anionic detergent in the spray-dried detergent granules can prevent the manufacture of a grain structure that is absorbent to a desired amount of a nonionic detergent, it may be preferable to manufacture spray-dried detergent granules of a type within this invention and mixing them with base beads of the invention onto which a nonionic detergent has been sprayed so that a larger amount of a nonionic detergent may be present in the final product. Varying ratios can be used to accomplish this, e.g. 1: 10 to 10: 1, 1: 5 to 5: 1 and 1: 2 to 2: 1 of the mentioned components, depending on the desired properties of the final product. Set is desirable that the bulk weights of the grains prior to mixing are approximately equal, preferably within 0.1 g / cm of each other, and that the grain sizes are approximately the same, normally located in the range having a sieve value of 2.00 - 0.1U9 mm, in order to prevent sifting and separation of the final mixture.

Amounts of additives and processing aids in the base granules and the spray-dried detergent will normally be limited to 20% thereof, preferably 1 to 10%, and most preferably 3 to 7% thereof. The amounts of processing aids, when using magnesium sulfate and citric acid, will usually be from 0.5 to 2% of magnesium sulfate, preferably 1 to 1.5% thereof, and 0.1 to 0.5% of sodium citrate, preferably 0 1 to 0.3% thereof. As for colorants, pigments and fluorescent brighteners, such substances are present, the amounts will usually be from 0.05 to 0.6% color pigment, such as ultramarine blue, preferably 0.2 to 0.1%, and 0, 1 to k% fluorescent brightening agent, preferably 1 to 3% thereof. The amount of titanium dioxide (a whitening pigment) will usually be from 1 to 3%, preferably from 1.5 to 2.5%. When a coloring dye or dyes is (are) used in place of a coloring pigment, the amounts thereof will usually be 1 to 50%, especially 5 to 20%, of that of the coloring pigments.

As for the preferred spray-dried granules of this invention, which may contain NTA or polyphosphate builders with or without synthetic organic detergents, or which may contain such detergent together with any of the compounds of the aforementioned list of preferred water-soluble builder salts, the bulk density is in the range of 0.2 to 0.8 g / cm, the aluminosilicate is hydrated zeolite A, the bentonite contains at least 3% moisture based on the anhydrous benzene. tonite, the water-soluble silicate, if present, is sodium silicate with a ratio of FegO: SiOg in the range of 1: 2 to 1: 2.8, and the moisture content of the granules is from 3 to 12% thereof. When the granules contain HTA or other nitrilotriacetic acid sodium salt, with or without synthetic organic detergent, the bentonite: zeolite ratio is in the range of 1: 6 to 1: 2, that of HTA: zeolite in the range of 1: 2 to 2: 1, and that of bentonite: M! A in the range of 1: 6 to 1: 2, and the percentages are hydrated zeolite, bentonite, sodium nitrilotriacetate and silicate, respectively. located in the ranges from 10 to ^ 0%, 2 to 25%, 10 to ho% and 0 to 5% · 8200805 23

When the preferred NTA-containing granules also contain a synthetic anionic organic detergent, with the aforementioned zeolite A, bentonite and moisture, and with or without soluble silicate, they preferably comprise 5 to 30 # synthetic anionic organic detergent, which will be sodium linear alkylbenzene sulfonate, in which the alkyl group contains 10 to 18 carbon atoms, sodium fatty alcohol sulfate, in which the alcohol contains from 10 to 18 carbon atoms, or sodium fatty alcohol ethoxylate sulfate, in which the fatty alcohol contains from 10 to 18 carbon atoms Contains 30 ethylene oxide groups per mole, or a mixture comprising 10 or more thereof, the water-soluble builder is a sodium salt of nitrilotriacetic acid (HTA), the ratio of bentonite: zeolite is in the range of 1: 6 to 1 : 1, the ratio NTA: zeolite in the range from 1: 3 to 3: .1, the ratio bentonite: NTA in the range from 1:10 to 1: 1, and the ratio 15 syntheti organic anionic detergent: zeolite ranging from 1: 1 to 1: k, and the percentages are hydrated zeolite, bentonite, sodium nitrilotriacetate, synthetic anionic organic detergent and silicate, respectively. located in the ranges from 10 to h0% 3 2 to 25 #, 10 to h0%} 10 to 25 # (more preferred area), and 0 to 5 #.

For phosphate-containing granules, with or without the synthetic detergent, the materials and proportions are the same as for the corresponding NTA-containing granules, except that penta sodium tripolyphosphate or tetrasodium pyrophosphate or a mixture thereof is present instead of NTA , but the percentages are then situated in the areas of resp. 15 to 35 #, 5 to 20 #, 15 to 0% and 0 to 5 #. Analogously, for the phosphate-containing granules with anionic detergent also present, the materials and proportions are the same as for the corresponding NTA-containing granules, and the percentage ranges are the same, except for that for the total polyphosphate, which 30 to 50 #.

The ranges of the ratios of the various base grain components in the final detergent composition, when a non-ionic detergent (possibly with other materials) is added afterwards, can be easily calculated from those indicated for the base grains less the amounts of the detergent and other materials added to the granules afterwards. 8200805 2 b. Conversely, the granular component ratios (and hence the recipe of the crank mixture) can be calculated back from the composition of the final product. Thus, e.g. calculating the recipe areas of the final product from the grain regions, when the final detergent composition contains only nonionic detergent added thereto, so that the final product contains 20% nonionic detergent, from the various ranges given for components in the base grain ratios of ratios thereof in the final detergent composition product, can be calculated by multiplying by 0.8, i.e. (100-20) / 100. Similarly, when the ratio of nonionic detergent (in formulas in which it is the sole additive to the grain) can be from 8 to 25% of the detergent composition, the multiplication factors will be from 0.92 to 0.75. The final percentage of non-ionic detergent in the product will be in the range of 8 to 30%, preferably 10 to 25%, and most preferably 15 to 22%, e.g. about 20%, but in some situations, for certain types of products, amounts in the range of 8 to 13% may be preferred. Usually the percentage of fragrance in the final product will be in the range from 0.1 to 1%, preferably from 0.2 to 0.%, the percentage of enzyme will be from 0.5 to 3%, preferably from 1 to 2%, and when an aqueous sodium silicate is added afterwards, the amount thereof will usually not be less than 1% and preferably limited to about 5% *, although in some cases even up to 10% has been used. When a softener is present in the final product, the amount thereof will usually range from 3 to 12%, preferably from 5 to 10%.

The base granules and spray-dried detergent granules of the invention are spray dried from an aqueous crank mixture, usually containing from about 50 to about 70 or 75% solids, preferably from 50 to 65% thereof, the balance being water, preferably demineralized water, as previously described (but tap water may also be used). The crank mixture is preferably prepared by successively adding various components thereof in a manner that will lead to the most miscible, easy to pump and non-sagging slurry for spray drying. The order of addition of materials can be varied depending on the conditions, but it is highly desirable to add the silicate solution (if used) last and if not last to add them. then add at least after the addition of some gelling or solidification preventing combination of% materials and processing aids such as citric acid and magnesium sulfate. It is usually preferred to add all or substantially all of the water first to the crank mixer, preferably at about the processing temperature, after which the processing aids (if any), and other minor components, including pigments and fluorescent brighteners and polyacrylate, if present, are added, followed by the zeolite, the water-soluble builder, anionic detergent (if present), bentonite, and silicate (if any). During such additions, each component will usually be vigorously mixed before the next component is added, but the addition methods can be varied depending on the conditions such that joint additions, where practicable, become possible. Sometimes additions of components can be made in 2 or more parts, and sometimes different components can be premixed before adding them in order to speed up the mixing process. Usually, the mixing speed and mixing power are increased when the materials are added. Small speeds can e.g. be used until after the addition of the last part of the zeolite or soluble builder to be mixed, after which the speed can be increased to medium and then to large, which speed is preferably used before, during and after the addition of only silicate solution.

The temperature of the aqueous medium in the crank mixer is usually about room temperature or a higher temperature, usually in the range of from 20 to 80 ° C, preferably from 30 to 75 or 80 ° C, most preferably from 1 + 0 to J0 ° C. Heating the crank mixing medium can promote the dissolution of the water-soluble salts of the mixture and thereby improve mixing, but the heating treatment, when performed in the crank mixer, can slow production rates and sometimes aid solidification of the mixture. An advantage of the presence of processing aids in the mixture (especially if some soluble silicate is present) is that they ensure that non-gelling slurries are obtained at higher or lower temperatures. Temperatures higher than 80 ° C (and sometimes higher than T0 ° C) will usually be avoided because of the possibility of decomposition of one or more of the components of the crank mixture, e.g. sodium bicarbonate. Lower temperatures of the crank mixture also in some cases raise the upper limits of the solid contents in the crank mixture, probably due to the insolubility of normally gelling or solidifying components.

Mixing times used in the crank mixer to obtain a good slurry can vary within wide limits, ranging from as little as 5 minutes in small crank mixers and for a slurry with a fairly high moisture content, to in some cases even U hours. The mixing times required to mix all components of the crank mixture substantially homo-15 together into an environment can sometimes be as little as 10 minutes, but in some cases may be up to 1 hour, although 30 minutes is a preferred upper limit is. When such initial mixing times are taken into account, normal crank periods will be from 15 minutes to 2 hours, e.g. 20 minutes to 1 hour, but the crank mixture should be such that it is mobile, non-gelling or setting for at least 1 hour, preferably for 2 hours, and most preferably for b hours or longer after the completion of the preparation of the mixture, and is preferably mobile for 10 to 30 hours before pumping out to the spray tower, to allow for situations where other manufacturing problems can be taken into account.

The slurry formed in the crank mixer, in which the various salts and all other components thereof are dissolved or evenly finely divided in particulate form, is conventionally transferred to a spray-drying tower, which is normally placed next to the crank mixer.

The slurry is fed from the bottom of the crank mixer to a positive conveying pump, which presses the slurry at high pressure through nozzles located at the top of a conventional spray tower (countercurrent or direct current), in which the droplets of the slurry pass through a hot drying gas, usually the combustion products of liquid roast or natural gas, in which the droplets are dried in the desired granular form. During drying, part of the bicarbonate (if 8200805 27 is present) can be converted to carbonate, releasing carbon dioxide, which, together with any polyacrylate, which is present in the mixture to be dried, is the physical properties of the granules to be produced. so that they are more absorbent to liquids, such as liquid non-ionic detergent, which can be sprayed onto those granules afterwards. However, the zeolite, bentonite and polyphosphate components (if any) of the base grains produced have also been found to favor liquid absorption and strong grain fabrication, and the polyacrylate improves grain properties and promotes faster drying, thereby increasing tower efficiency. improved.

After drying, the product is sieved to the desired dimensions, e.g. a mesh size of 2.00 to 0.250 or 0.1 i + 9 and is then ready to spray a non-ionic detergent thereon, when it is a base granule composition, with the granules either in a hot or cooled (room temperature) state. However, the nonionic detergent will usually be at a higher temperature, such as a temperature from 30 to 60 ° C, e.g. 50 ° G, in order to ensure that it is liquid; nevertheless, after cooling to room temperature, it will preferably be solid, often resembling a waxy solid. Even when the nonionic detergent is slightly tacky at room temperature, this property does not smooth the final composition poorly because the detergent penetrates below (or into) the grain surface. The nonionic detergent, which is applied to granules, in motion or tumbling, in the form of a mist or as droplets in a known manner, is preferably a condensation product of ethylene oxide and a higher fatty alcohol, as previously described, but other non-ionic substances may also be effective. The enzyme preparation (referred to herein as enzyme, although it is recognized that it also contains a carrier material), hydrous silicate and any other powdered additives may be sprayed onto the detergent eggs, and fragrances as well as any other liquids to be added afterwards be sprayed at a suitable point before or after addition of the powder or powders.

The spray dried detergent, the spray dried base granules and the detergent compositions made therefrom contain little or no silicate from the crank mixture, although some amount of solid silicate may be added afterwards. The powdered silicate added afterwards, when used, does not seem to react as much with the zeolite, so that the formation of agglomerates of zeolite 5 and silicate, which tend to deposit on laundry, is counteracted when compared with deposits from products where silicate was added in the crank mixer. Although, without the presence of the bentonite, silicate would normally be used because of its grain-controlling and anti-corrosion effects, the present detergent compositions produce acceptable grains and have not been shown to cause corrosion of aluminum articles. Furthermore, the bentonite does not adversely affect the stability of the product and in fact appears to help to keep the granules together and thus make them resistant to crushing and pulverization during transportation and use. The presence of the bentonite significantly improves the properties of the final detergent composition by providing greater calcium ion binding and less zeolite deposition on washed fabric. When the low molecular weight polyacrylate is present, the base grains 20 become more porous and more absorbent to the liquid nonionic detergent without undesirably reducing the bulk density of the product. When one considers that bentonite is a clay and serves as a binder, it could be expected to cause deposition and gelling problems on its own. Therefore, the reduced deposition properties, the absence of gelling and the easy dispersibility of the product are surprising and these properties are important results of the present invention. Important results of the presence of the small amount of polyacrylate in the spray dried granules can also be considered the improved spray drying of the present base granules and detergent compositions, as well as the improved uptake of liquid non-ionic detergent by the base granules.

The invention is further illustrated by the following examples, which have no limiting meaning. Unless otherwise indicated, both in the examples and in the description, all temperatures are in ° C and all parts are in parts by weight.

8200805 29

Where amounts and proportions of zeolite have been reported, they are intended for the normal hydrate form used, because the hydrated water of the zeolite is considered not to leave the zeolite and not become part of the aqueous solution medium in the present operations in the crank mixer. Also, some of the water present in the base granules and the detergent compositions is present as hydrate water of the zeolite. Likewise, the moisture associated with the bentonite can also be considered as not free moisture, but because of the smaller percentage present, this distinction can often be neglected in practice.

Example I (comparative example)

A portion consisting of 100 parts crank mixture for spray drying base grains, considered satisfactory for later conversion to a detergent composition by adding synthetic nonionic organic de-tergent thereto, was prepared by adding to the crank mixer + 7 parts demineralized water at adding a temperature of about 27 ° C and then successively, and initially at a low mixing speed in the crank mixer, to be mixed therewith 1.0U parts Tinopal 5BM extra concentrated (Ciba-Geigy), 0.13 part ultramarine blue powder 0.07 part sodium polyacrylate (Alcosperse 107D), 21.11 parts Linde hydrated zeolite kA (20% crystal water), 6.25 parts Mineral Colloid no.

1 (bentonite), 15.75 parts of sodium bicarbonate (technical grade), 7.7 * + parts of sodium carbonate (technical anhydrous soda), and 0.91 parts of titanium dioxide (anatase). During the mixing of the various components, the mixing speed was increased to medium and finally to high and after adding all the ingredients, which took about 15 minutes, mixing was continued for about 1 hour (in some cases up to b hours of mixing can take place ), during which time part of the water present, e.g. about 2 to 6 parts, could be lost by evaporation and replenished if desired. During the mixing time, the slurry in the crank mixer was always mobile and that slurry did not gel, solidify or form a cake. Since bicarbonate partially decomposes into carbonate during spray drying, the amounts of bicarbonate and carbonate in the composition contained in the crank mixer may be varied depending on the operating characteristics in the spray tower *.

8200805 30

Starting from about 5 minutes after all the components of the crank mixture were present, the mixture was drained from the crank mixer to a pump, which pumped at a pressure of about 21 kg / cm to the top of a counterflow spray tower wherein the initial temperature was about 430 ° C and the final temperature was about 105 ° C. The substantially inorganic base granules obtained had a bulk density of about 0.6 to 0.7 g / cm, an initial tack of less than $ 10, a particle size range generally comprised between 2.00 and 0.250 mm (they were thus sieved ), 10 and a fineness characteristic (through a 0.297 mm screen) of about 15 $. The moisture content of the granules was in the range of 1 to 10 $, usually closer to 10 $, e.g. 8 to 10 $. These base granules were found to be free-flowing (flow value 80 $), non-sticky, sufficiently porous, yet strong on the surface thereof. They were able to easily absorb significant amounts of liquid non-ionic detergent without becoming unacceptably tacky.

Detergent products were obtained from the spray dried granules by spraying a normal waxy nonionic detergent on the surface of the tumbling granules. Feodol 23-6.5 was used, but Feodol 23-7 or Feodol 25-7 (and sometimes Feodol 45-11) can also be used instead. The non-ionic detergent was in a hot liquid state (at a temperature of about U5 ° C). The amount sprayed was such that a final product containing about 20% nonionic detergent was obtained.

Proteolytic enzyme "(Alcalase, 1.7T or Maxazyme 375) was applied in powder form to give a concentration of 1.5% thereof in the product, and fragrance was sprayed on the product to obtain a concentration of 0.25 The resulting detergent compositions had a bulk density of about 0.7 to 0.8 g / cm and contained about 32.45% zeolite (hydrated), 19.7% of the nonionic detergent, 18.5% sodium carbonate (part of it came from decomposition of sodium bicarbonate), $ 30.5 sodium bicarbonate, $ 1.3 free water, $ 1.4 enzyme, $ 1.6 fluorescent brightener, $ 0.25 fragrance, $ 0.2 ultramarine blue, 9.6 $ bentonite, 0.1 $ sodium polyacrylate, and 1.4 $ Ti-35 tan dioxide.

The detergent manufactured according to the above re 8200805 ** s 31 cept is an excellent detergent for very dirty laundry and is especially suitable for washing domestic laundry in automatic washing machines. it is physically and aesthetically beneficial and attractive because it is not dusty and extremely free-flowing, allowing it to be packaged in glass bottles and narrow-necked plastic bottles from which it can be easily poured for use. The manufactured detergent compositions containing bentonite as described had better binding properties for calcium ions, but more importantly they left less zeolite residue on laundry washed well (in an automatic washing machine at usual concentrations for such products and at normal washing temperatures), especially when that laundry was line dried, than did similar compositions containing less bentonite and sodium silicate being present in the spray dried base beads. This difference is amplified when the wash water has a high hardness, e.g. 200 ppm, if calcium carbonate, the wash water is cold and a moderate speed is applied.

The base granules and detergent composition produced have acceptable standard properties with which the further granules and detergent compositions described in the following examples can be compared, and to which they prove beneficial. Also, the manufacturing methods are essentially the same and appear to be satisfactory.

In a normal mode of operation, the crank mixtures 25 will be manufactured quickly and discharged from the crank mixer just as quickly; sometimes they are even manufactured in just 5 minutes and pumped out of the crank mixer in just 10 minutes. Still, it is often important that the present blends resist being left in the crank mixer for at least 1 hour without gelling or solidifying, because such time delays sometimes occur in commercial manufacture. The described crank mixture can be stored for b hours, and often considerably longer, without gelling or solidifying, which is at least in part due to the bentonite content and the absence of silicate. This action of the bentonite 35 is unexpected because it also exerts a thickening effect on the crank mixture, but although the mixture may become noticeably thicker, it remains pumpable. Minor components of the crank mixture, such as the fluorescent brightener and pigment, can be omitted therefrom and enzyme as well as fragrance can be omitted from the final product, although it is highly preferred that all such materials be present. The temperature of the crank mixture can be modified, such as by raising it to 52 ° C, and the amounts of the various components can be varied by + 10 #, + 20 # and + 30 $ while still being within the previously given limits remain and yet useful mixtures will be available, leading to the desired granules and detergent compositions. The solids content of the crank mixture may. be varied over the indicated range, e.g. up to k5f and 65 #, yet good mixing and spray drying is obtained. Other, order of addition of components to the crank mixer may be used, but it is usually desirable to add any silicate last or near last, and it is preferable to add the bentonite only late in the process. , preferably just for the silicate. Instead of using Zeolite b-A, Zeolite X and Y can also be used, just as other types of Zeolite A can also be used. Although it is preferred to use the about 80 # hydrated Zeolite kA (moisture content of about 20 #) according to this example, various degrees of hydration of the zeolite are acceptable and in some cases substantially anhydrous crystalline zeolites or amorphous zeolites can be used. Varying the amount of bentonite within the indicated range to J%, 13 # and 19 # in the base grain, eg, still leads to useful products, but those containing larger amounts of bentonite will usually be more effective to contribute to prevent zeolite deposits on the laundry. In some instances, it may be desirable to use even high percentages of bentonite within the limits set forth herein, thereby ensuring that the remaining components of the base bead will be such that the beads will be free flowing and active detergents. The amount of bentonite suitable for commercial use depends on a number of factors and will normally equate to a balance between the desired reduction in zeolite residue and the desired building effects and other functional effects of other detergent composition components. , which can be applied in place of a larger amount of bentonite.

The improvement observed in the detergent compositions of this example, in the form of depositing less residue on the washed material, was examined by comparing the described product with a control product of substantially the same composition, but in which no bentonite was present and containing about 8% sodium silicate in the final product. In this review, a "Whirlpool Suds Saver" model washing machine was used with 8 minute wash times on a gentle wash cycle. The concentration of the detergent composition was 0.06 $, the wash water contained calcium and magnesium with a total hardness of 200 ppm, as calcium carbonate, and the temperature of the water was 2k ° Q, The wash data was as follows: 100 $ cotton ; 100 $ polyester; 85 $ acetate and 15 $ nylon; 15 and 65% polyester and 35 $ cotton. The wax was judged wet and after line drying (line drying usually results in a more discernible residue than drying with an automatic tumble dryer). No residue was observed in that case. When the detergent composition was tested according to the control recipe, a moderate residue was observed on all the washed species.

The results of the test for determining the actual residue described above were tested by weighing the residue deposited on a twill cotton test fabric. In carrying out that test, the detergent composition of the invention was filtered through a sample of twill cotton, the detergent being in solution suspension at a concentration of 0.12% in water with a hardness of 200 ppm (as CaCO3) at 21 ° C, and the weight of the residue on the cloth was determined and compared. In such a test, the percentage of residue compared to the control 30 test was about 75% which is considered to be a significant difference in the appearance of washed products.

The aforementioned adhesion test, in which the tackiness of detergent product is determined, is a test in which 10 g of basic granules (or in some cases detergent composition) are uniformly applied between 2 watch glasses, both of which have a diameter of 23 cm and a weight of 500 g on the top watch glass becomes 8200805 V>

3U

(both watch glasses are concave at the top). After 5 minutes, the weight on the top watch glass is removed and the bottom watch glass is turned over, after which the product adhering to that watch glass is weighed. The percentage of adhesion is the 5 grams of product remaining on that watch glass multiplied by 10.

The flow index is determined by a flow test, comparing the volumetric flow of base grains (and in some cases of the final product) and standardized Ottawa sand (-20 + βθ, 10 US sieve range) by measuring the times required are to get a Mason bottle of. 1.9 L by emptying a round hole with a diameter of 2.2 cm, which is located in a spout, which is attached to its lid. The percentage flow index is the flow time for the sand divided by the flow time for the test product multiplied by 100.

Example II

Basic granules such as those of Example I, but with NTA incorporated therein instead of a portion of the carbonate and bicarbonate, were made in much the same manner as described in Example I.

The composition was changed only by replacing 5 parts of the zeolite, 12 parts of the sodium bicarbonate and 3 parts of the sodium carbonate in the crank mixer with 20 parts of NTA, as trisodium salt monohydrate. The NTA was added after the sodium carbonate during the mixing treatment. The base granules obtained were not as friable as those of Example I, but were still sufficiently free flowing.

Sufficiently, the final detergent composition contained 12% nonionic detergent instead of $ 19.7, while the final percentages of the remaining components were increased accordingly. The product obtained was a satisfactory particulate detergent with a powerful action.

According to variations of this formulation, 2.5% aqueous sodium silicate was added afterwards to the product in view of its anti-corrosion properties and because of its activity to bind magnesium ions in the wash water. When the silicate has approximately the same particle size and density, it is not screened or separated from the other components of the detergent granules during transportation and storage, and the product obtained conforms to the specifications for 8200805. powerful detergent commercial detergent; however, a small amount of zeolite silicate aggregate can be observed on the washed materials.

According to another recipe, 3L of sodium silicate with a ratio: SiOg of about 1: was incorporated into the final product by adding an aqueous solution thereof in the crank mixer together with 1.5% magnesium sulfate and Q, h% citric acid, to prevent gelation and solidification in the crank mixer. The final product was a good detergent with powerful action, but resulted in the deposition of more zeolite silicate aggregate on washed line-dried materials than was the case using a similar recipe, using the aqueous sodium silicate was added afterwards.

Example XII

The procedure of Example II was repeated, but pentasodium tripolyphosphate was used instead of the HTA. The products obtained were good detergents with a bulk density of about 0.8 g / car (such as those of Example II), but such bulk density and can be varied by controlling the operating conditions in the spray dryer and the formulation so that bulk weights are obtained in the range of 0.7 to 0.9, and in some cases - bulk weights can even be reduced to 0.3 · With the silicate added afterwards, bulk weights can be slightly higher, especially for those in the lower section of the area. The product is more free flowing than that of Example II, but is approximately equivalent in terms of washing power.

In the recipe described above and. in those of the previous examples, an additional amount of bentonite may be added to the crank mixer to produce products containing 15% (or 30 more) bentonite. Such products are even better in binding effects, dispersibility and other desirable properties attributable to the bentonite, and are good detergent (and base grain) formulations. Also, the tripolyphosphate may be wholly or partly, e.g. half, are replaced with tetrasodium pyro-phosphate and thus equally good products are obtained.

8200805 36

Example IV

A final detergent product was prepared essentially according to the method of Examples I and II and contained 30 parts of the zeolite, 30 parts of NTA, 20 parts of the nonionic substance, 10 parts of bentonite, 5 parts of sodium carbonate, 5 parts water and 1.3 parts of enzyme. This product had a density of about 0.5 g / cm and was a satisfactory detergent. However, in order to improve the flowability of the product, it is desirable to reduce the nonionic detergent content to $ 15 and preferably to $ 12. To increase the bulk density to about 0.7, half of the bentonite can be replaced with sodium silicate (Na2O: SiO2 ratio is 1: 2.4), which is added to the crank mixer as a final component as a ^ 7 Accordingly, 1.5% aqueous solution, and 1.5 parts magnesium sulfate as well as 0.1 part citric acid can be added previously as anti-gelling agents when preparing the crank mixture. The resulting product has a bulk density of about 0.7 g / cm and can absorb about 20 parts of non-ionic detergent without thereby becoming tacky or less flowing. Although the product deposits less zeolite-silicate agglomerate than compositions with customary larger amounts of silicate present from crank additions, the agglomerate can be observed on laundry that has been washed with the product and line dried.

Example V

Instead of making base granules to which detergent 25 is applied to form a detergent composition, the composition can be spray dried directly from the crank mixer while incorporating a suitable synthetic organic detergent into the crank mixture. Using substantially the same procedures as described in Example 1, a crank mixture was formulated, which was spray dried to detergent granules, containing 16 parts linear tridecylbenzene sulfonate, 20 parts zeolite, 12.5 parts bentonite, 15 parts UTA, Contains 10 parts of sodium carbonate and conventional additives (colorant, fluorescent brightener). The bulk density of the spray-dried product is in the range of 0.3 to 0.8, norma-35 liters is located in the lower part of that range and is sometimes as low as 0.2 g / cm. In the manufacturing process, the organic de- 8200805

3T

normally added after the water. Drying is usually performed to a moisture content of about 8 to 12%. The product obtained preferably had about 3 parts of post-added aqueous sodium silicate, together with other conventional additives, such as enzyme and fragrance. It is a powerful, satisfying detergent that does not leave unwanted amounts of zeolite or zeolite silicate aggregate on the washed fabric. Due to the presence of the hentonite, the detergent appears to disperse very quickly when added to the wash water, and it is believed that at least in part this rapid dispersibility can coexist with the presence of the hentonite. are attributed to prevent the deposition of zeolite.

Example VI

The procedure of Example V was followed, but the NTA 15 was replaced with an equal amount by weight of anhydrous soda. Such a product also provides sufficient detergent with a powerful action.

Example TL1

The procedure of Example V was followed, but penta-20 sodium tripolyphosphate was added in place of NTA. In particular, the product obtained was free-flowing and was a good synthetic organic detergent composition with very powerful action. Although when silicate is to be present, it is preferred that it be added afterwards as aqueous sodium silicate, up to 5 parts of silicate can be added to the crank mixer along with the appropriate amounts of magnesium sulfate and citric acid, as described in the previous examples, and Useful detergent compositions will be obtained, although some zeolite silicate deposition will occur.

In addition to the usual materials which can be added afterwards, the product of this example (to the products of other examples) may contain softening amounts of a cationic material, e.g. Q% dimethyldistearylammonium chloride, an amphoteric detergent, e.g. 5% Miranol CgM (1-carboxymethyl-1-carboxyethoxy-35 ethyl-2-coco-imidazolinium betaine) or a bleach, e.g. 15% sodium perborate (preferably activated) is added. Of course you will- 8200805 f * 38

When the additions of such materials reduce the amounts of the remaining components in the final composition and thereby slightly alter the properties of the compositions, sometimes more product is needed in the wash water to achieve the same wash effect.

In Examples V - VII, the linear tridecylbenzene sulfonate may be replaced by an equal amount by weight of sodium lauryl sulfate or sodium lauryl polyethoxy sulfate (3 to 10 ethoxy groups) or mixtures of such materials in equal parts, and the products obtained are also "useful as detergent compositions In an analogous manner, instead of NTA, carbonate, carbonate and bicarbonate, and polyphosphate, sodium citrate and / or sodium gluconate can be substituted, at least in parts, eg 1A, 1/2, and good detergents are obtained.

15 Example VIII

The products of Example I and Example VII (the first described main products) were mixed in an equal amount to obtain a final product having the properties of the two constituents. Before mixing, the materials to be mixed both had substantially the same bulk density, about 0.5 g / cm and about the same particle size, in the range of a sieve value of 2.00-0.250 mm, in order to prevent separation during transport and storage . The blend product was particularly useful for removing both oil-based and clay-based laundry soils and was free-flowing, stable and attractive. In some cases, one of the particulate starting materials may be colored or pigmented and the other may be left in natural color to obtain special effects in appearance. In addition to the particle sizes and bulk weights being approximately equal, it is preferred that the moisture content is also approximately equal, e.g. about $ 10, so that a little migration of moisture between the different grains can occur.

In the materials used in Example VII, the anionic detergent, consisting of sodium alkylbenzene sulfonate, may be replaced by a sodium α-olefin sulfonate (1U - 15 carbon atoms in the olefin group) or by a sodium paraffin sulfonate (12 - 15 carbon 8200805). * 39 atoms in the paraffin) and the mixtures produced will also be useful detergents.

Example IX

By essentially following the procedure described in Example I 5 »a stool mixture was composed of 36.9 parts of water, 1.2 parts of fluorescent brightening agent (Tinopal 5BM, extra concentrated), 0.1 part of ultramarine blue, 2.1 parts of magnesium sulfate (hepta hydrate), 0.3 part sodium citrate, 22, U parts zeolite kA powder (partly hydrated to about 20% moisture content), 20.9 parts tri-10 sodium nitrilotriacetate monohydrate, 7 parts of a solution of sodium: silicate with hj, 5% solid (Na 2 O: SiOg = 1: 2, k), 3.0 parts sodium bentonite (formerly commercially available under the name Thixo-Jel No. 2), 2.5 parts , technical anhydrous soda and 2.1 parts of a mineral compound, which can increase the grain porosity, as builder dust. The crank mixture was spray dried in a manner as previously described, the moisture loss during drying being approximately $ 5.2.

20 parts of Heodol 23-6.5 were sprayed onto 78 Λ parts of the spray dried base granules with particle sizes in the range 2.00 - 0.1 ^ 9 mm (sieved), after which the granules were mixed with 1.3 parts of a. highly active proteolytic enzyme, and 0.3 part detergent perfume was sprayed thereon. The final product had a zeolite content of $ 25, an HTA content of $ 30, a sodium bentonite content of $ 5, and a solid content of water-soluble sodium silicate of $ 5. The moisture content was $ 5 and the active detergent ingredient (polyethoxylated higher fatty alcohol) content was $ 20.

3

The bulk density was about 0.7 g / cm and the pH of a $ 1 solution was about 10.

The detergent composition prepared by this method was a satisfactory non-ionic detergent with high performance, but deposited slightly more zeolite silicate aggregate on line-dried laundry than was the case with a similar composition, which was manufactured without the presence of any water-soluble silicate as a solid material. It is preferred that such a similar composition also contains about 0.1 to 0.5% of low molecular weight sodium polyacrylate, of the 8200805

Uo type as previously described herein. Both products have a good washing effect on laundry and are especially effective when washing with cold water, which is at least partly due to the bentonite content present and the almost instant dispersion, which is observed when the detergent becomes wash water. (which rapid dispersion also shortens the time for any reaction between soluble silicate and zeolite to form aggregates to be avoided as undesirable).

* \ 8200805

Claims (23)

1. Free-flowing, spray-dried granules useful as a detergent or for the manufacture of a particulate built-up synthetic, nonionic organic detergent composition, which detergents have reduced particle deposition properties due to the presence of bentonite and low content of water-soluble silicate or the absence of such silicate in the spray-dried granules, comprising, by weight, from 5 to 60% water-softened alumino silicate, 2 to 40% bentonite, which contains sufficient moisture "to disperse the" bentonite in order to counteract deposition of aluminosilicate on the "to be washed", facilitate 5 to 60% water-soluble "builder or mixture of such builders, 0 to 30l water-soluble synthetic organic detergent and 0 to 5% in water soluble silicate. Granules according to claim 1, characterized in that when water-soluble synthetic detergent is not present, the water-soluble builder polyphosphate, pyrophosphate, orthophosphate, borate, nitrilotriacetate, gluconate or citrate or a mixture of 2 or more thereof. Granules according to claim 2, characterized in that they have a bulk density in the range from 0.2 to 0.9 g / cm and particle sizes in the range from 2.00 - 0.1 ^ 9 mm, wherein the water softening aluminosilicate is a hydrated water softening zeolite containing from 15 to 25% by weight of hydrate water and having an exchange capacity for calcium ions ranging from 200 to kOO mg equivalent of calcium carbonate hardness per gram anhydrous zeolite, the bentonite is a swelling clay with a swelling capacity, in water, O of 3 to 15 cm / g and a viscosity of 3 to 30 cP at a concentration of 6% in water, and containing at least 2% moisture based of an anhydrous bentonite, a water-soluble builder is present, which is poly-phosphate, pyrophosphate, orthophosphate, borate, nitrilotriacetate, citrate, gluconate, carbonate or bicarbonate or a mixture of 2 or more thereof, and the water-soluble silicate an alkali metal. (M) silicate with a ratio of MgO: SiO4 in the range from 1: 1.6 to 1: 3. 8200805 k2 1 *. Granules according to claim 3, characterized in that the ratio of bentonite to zeolite is in the range from 1: k to 1: 2, the ratio of water-soluble builder to zeolite is in the range from 1: 2 to 3 ·· 1 and the ratio of bentonite to 5 water soluble builder is located in it. range from 1:10 to 1: 1. Granules according to claim k3 with. characterized in that those grains comprise from 10 to 10% hydrated sodium zeolite, 2 to 35 # bentonite, which. bentonite is of one type which has a swelling capacity in the range of 7 to 15 cm / g and a viscosity. in the range of 8 to 10 3 C cP at a concentration of 6% in water, 10 to 50% water-soluble alkali metal builder salt or mixture thereof, 0 to 25% water-soluble synthetic anionic detergent, and 0. to 3% water-soluble silicate. Granules according to claim 5, characterized in that they comprise 15 granules of 15-35% Zeolite A, 5-20% improved Wyoming bentonite, 2.0-50% in. water soluble sodium house salt or mixture thereof, 0 to 20 # water soluble synthetic anionic organic detergent and 0% sodium silicate, and in which the bentonite: zeolite ratio is in the range of 1: 3 to 2: 3, the ratio in 20 water soluble builder: zeolite in the range from 2: 3 to 2: 1, and the bentonite: water-soluble builder ratio in the range from 1: 6 to 1: 2. Granules according to claim 2, characterized in that the water-soluble builder is selected from the group formed by carbonate, bicarbonate, polyphosphate or nitrilotriacetate or a mixture thereof, and the bentonite contains at least 3% moisture based on the anhydrous bentonite. Grains according to claim 7, characterized in that the bentonite contains at least k% moisture, the water-soluble builder consists of nitrilotriacetate, and no water-soluble synthetic organic detergent nor any water-soluble silicate is present. is. Grains according to claim 8, characterized in that said grains comprise from 15% to 10% of hydrated Zeolite A, which contains 15 to 25% by weight of hydration water thereof and has an exchange capacity of calcium ions in the range of 200 up to UOO mg equivalents of calcium carbonate hardness per gram of anhydrous zeolite, 10 to 8200805 - · 20 $ bentonite, which is an improved Wyoming bentonite with a soul power in the range of 7 to 15 ml / g and having a viscosity in the range of 3 to 30 cP at a concentration of $ 6 in water, and 20 to 60 $ NTA. Granules according to claim 7, characterized in that the bentonites. contains at least k% moisture, the water-soluble builder comprises polyphosphate, and no water-soluble synthetic organic detergent nor water-soluble silicate is present. Granules according to claim 10, characterized in that they comprise 10 granules of 20 to 20% hydrated Zeolite A, containing 15 to 25% by weight thereof of hydration water and having an exchange capacity for calcium ions in the range of 200 up to hOO mg equivalents of calcium carbonate hardness per gram of anhydrous zeolite, 10 to 20 $ bentonite, which is an improved Wyoming bentonite with a swelling capacity of 3 to 15 cm / g and a viscosity in the range of 3 up to 30 cP at a concentration of 6 $ in water, and 20 to 60 $ wet rium tripolyphosphate, Grains according to claim 2, characterized in that said grains comprise from 5 to 30% water-soluble synthetic organic detergent. Granules according to claim 12, characterized in that the water-soluble synthetic organic detergent is an anionic detergent. th. Granules according to claim 13, characterized in that the anionic detergent contains sodium linear alkylbenzene sulfonate, in which the alkyl group contains 10 to 18 carbon atoms, sodium fatty alcohol sulfate, in which the alcohol contains 10 to 18 carbon atoms, or sodium fatty alcohol ethoxylate sulfate, in which the fatty alcohol contains 10 to 18 carbon atoms. and which contains from 3 to 30 ethylene oxide groups per mole, or a mixture of 30 is 2 or more thereof, and the amount of that anionic detergent in the granules is from 5 to 25%. Granules according to claim 7, characterized in that said granules comprise from 3 to 30% water-soluble synthetic anionic organic detergent. Granules according to claim 15, characterized in that the anionic detergent contains sodium linear alkylbenzene sulfonate, which contains the 8200805 kk alkyl group of 10 to 18 carbon atoms, sodium fatty alcohol sulfate, in which the alcohol contains from 10 to 18 carbon atoms, or sodium fatty alcohol ethoxylate sulfate, wherein the fatty alcohol contains from 10 to 18 carbon atoms and contains from 3 to 30 ethylene oxide groups per mole, or is a mixture of 2 or more thereof, and the amount of that anionic detergent in the granules is from 5 to 25%. Granules according to claim 7, characterized in that said granules contain neither water-soluble synthetic organic detergent nor water-soluble silicate. Granules according to claim 2, characterized in that said granules comprise from 0.05 to 1% polyacrylate with a molecular weight in the range from 1,000 to 5,000. * Granules according to claim 3, characterized in that said granules have a bulk density in the range from 0.2 to 0.8 g / cm, wherein the aluminosilicate is hydrated zeolite A, the bentonite at least 3% moisture based of the anhydrous bentonite, the water-soluble builder is a sodium salt of nitrilotriacetic acid, the water-soluble silicate, if present, is sodium silicate in a ratio: SiOg in the range of 1: 2 to 2: 2.8, the moisture content of the granules from 3 to 12% thereof, the bentonite: zeolite ratio is in the range of 1: 6 to 1: 2, the ratio of ITA: zeolite in the range of 1: 2 to 2: 1, and the ratio bentonite: ÏTA in the range 1: 6 to 1: 2, and the percentages of hydrated zeolite, bentonite, sodium nitrilotriacetate and silicate, respectively. are located in the ranges from 10 to h0%, 2 to 25 $, 10 to Ho% and 0 to 5%. Grains according to claim 3, characterized in that said O grains have a bulk density in the range from 0.2 to 0.8 g / cm, comprise 5 to 30% synthetic anionic organic detergent, and wherein the aluminosilicate is hydrated zeolite. A is, the bentonite contains at least 3% moisture based on the anhydrous bentonite, the water-soluble builder is a sodium salt of nitrilotriacetic acid, the synthetic anionic organic detergent sodium linear alkyl benzene sulfonate, which contains the alkyl group of 10 to 18 carbon atoms, sodium fatty alcohol 35 sulphate, in which the alcohol contains from 10 to 18 carbon atoms or sodium fatty alcohol ethoxylate sulphate, in which the fatty alcohol from 10 to 18 8200805 ** - -. Containing 5 carbon atoms and containing from 3 to 30 ethylene oxide groups per mole, or a mixture of 2 or more thereof, the water-soluble silicate, if present, is sodium silicate in a ratio of NagO: SiOg in the range of 1: 2 up to 1: 2.8, the moisture content of 5 grains is from 3 to 12 $ thereof, the bentonite: zeolite ratio is in the range of 1: 6 to 1: 1, the HTA: zeolite ratio is in the range of 1 : 3 to 3: 1, the ratio of bentonite: HTA in the range of 1: 10 to 1: 1, and the ratio of synthetic anionic organic detergent: zeolite in the range of 1: 1 to 1: k, 10 and the percentages of hydrated zeolite, bentonite, sodium nitrile triacetate, synthetic anionic organic detergent and silicate, respectively. are located in the ranges from 10 to ^ 0 $. 2 to 25%, 10 to H0 $, 10 to 25 $ and Q to 5 $ 21. Granules according to claim 3, characterized in that said granules have a bulk density in the range from 0.2 to 0.8 g / cm, the aluminosilicate being hydrated zeolite A, the bentonite containing at least 3% moisture based on the anhydrous bentonite, the water-soluble builder pentasodium tripolyphosphate or tetrasodium pyrophosphate or a mixture thereof, the water-soluble silicate, if present, is sodium silicate in a ratio Ha20: SiOg in the range of 1: 2 to 1: 2.8, the moisture content of the granules is from 3 to 12% thereof, the bentonite: zeolite ratio is in the range of 1: 6 to 1: 2, the total polyphosphate: zeolite ratio is in the range of 1: 2 to 2: 1, and the bentonite: total polyphosphate ratio in the range 1: 6 to 1: 2, and the percentages of hydrated zeolite, bentonite, total polyphosphate and silicate, respectively. are located in the ranges of $ 15 to $ 35, $ 5 to $ 20, 15 to $ 0% and $ 0 to 5 · 22. Granules according to claim 3, characterized in that said O granules have a bulk density in the range from 0.2 to 0.8 g / cm and comprise 5 to 30% synthetic anionic organic detergent, the aluminosilicate being hydrated zeolite A is, the bentonite contains at least 3% moisture based on the anhydrous bentonite, the water-soluble builder pentasodium tripolyphosphate or tetrasodium pyrophosphate or a mixture thereof, and the synthetic anionic organic detergent 35 is a sodium linear alkylbenzene sulfonate, wherein the alkyl group is from 10 to Contains 18 carbon atoms, sodium fatty alcohol sulfate, in which the alcohol contains 8200805 V - «k6 from 10 to 18 carbon atoms or sodium fatty alcohol ethoxylate sulfate, in which the fatty alcohol contains 10 to 18 carbon atoms and that contains from 3 to 30 ethylene oxide groups per mole, or a mixture comprising two or more thereof is water-soluble silicate, if present, is sodium silicate in a ratio of NagO: SiOg i n the range from 1: 2 to 1: 2.8, the moisture content of the granules from 3 to 12 # thereof, the ratio bentonite: zeolite is in the range from 1: 6 to 1: 1, the ratio total- polyphosphate: zeolite in the range of 1: 3 to 3: 1, the bentonite: total poly ratio. 10 phosphate in the range of 1:10 to 1: 1, and the ratio of synthetic anionic organic detergent: zeolite in the range of 1: 1 to 1: and the percentages of hydrated zeolite, bentonite, total polyphosphate, synthetic anionic organic detergent and silicate resp. are located in the ranges from 10 to 1 + 0 #, 2 to 25 #, 10 to 50 #, 10 15 to 25 # and 0 to 5 # Detergent composition, characterized in that said composition comprises granules according to claim 1, in which a non-ionic detergent is absorbed such that the percentage of the non-ionic detergent composition is in the range from 8 to 30 # . 20 2h. Detergent composition, characterized in that said composition comprises granules according to claim 2, in which a non-ionic detergent is absorbed such that the percentage of the non-ionic detergent in the composition is in the range from 8 to 30 #. 25. Detergent composition according to claim 2b, characterized in that the non-ionic detergent is a condensation product of 6 to 12 moles of ethylene oxide and a higher fatty alcohol with 12 to 16 carbon atoms, and the amount of that non-ionic detergent is in the composition located in the area From 10 to 25 #. 26. Detergent composition, characterized in that said composition comprises granules according to claim 17, in which a non-ionic detergent is absorbed such that the percentage of the non-ionic detergent in the composition is in the range of 8 to 30 #. Detergent composition according to claim 26, characterized in that the non-ionic detergent is a condensation product of 35 to 22 moles of ethylene oxide and a higher fatty alcohol with 12 to 16 carbon atoms, and the amount of that non-ionic detergent in the sa 8200805 vr composition is located in the range of 10 to 25%. 28. Detergent composition, characterized in that said composition comprises a mixture of granules according to claim 17 and a composition according to claim 26 and having particle sizes in the range from 2.00-0.1h9 mm in a weight ratio in the range from 1: 10 to 10: 1, and wherein the bulk density of the grains prior to mixing is within 0.1 g / cm of each other and the bulk density of the final composition is in the range 3 of 0 , 2 to 0.9 g / cm. 8200805