SE452629B - FLUID SPRAY DRIED PEARL MATERIAL AND DETERGENT COMPOSITIONS - 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

20 25 30 452 629 J people and recently the US authorities' disapproval of the use of NTA in detergents has been withdrawn. Although some non-phosphate-containing detergent compositions will continue to be manufactured for use in areas near lakes and rivers, which via the phosphate appear to be supplied with a nutrient required for algae growth so that the water becomes eutrophic, phosphate-containing compositions are now resold. and / or NTA. Although the zeolites, preferably Zeolite A and in particular hydrated Zeolite 4A, have been used as detergent salts in phosphate-free and NTA-free detergent compositions, they have also been found to be useful components in improved detergent and bead compositions containing phosphate (s). ) and / or NTA. Generally, about 6-12% water-soluble sodium silicate has been included in mixtures from which spray-dried bead material or detergent compositions are prepared. The silicate has been used due to its bonding effect with respect to the other components of the bead material, which bonding results in stable beads, and it has been found that it helps to give the beads an internal network structure. It also acts as an anti-corrosion additive, which prevents chemical attacks on the aluminum parts in washing machines and other utensils that may come into contact with the detergent solution. However, it has been found that at the previous levels of e.g. 8-10% in the final product, the combination of water-soluble silicate and zeolite in the mixture leads to the formation of aggregates of these materials in the spray-dried beads, which aggregates give undesired deposits on washed material, whereby its colors are adversely affected. By practicing the present invention and using certain levels of zeolite, bentonite and water-soluble detergent salts and a small quantity or no water-soluble silicate, spray dried beads with sufficient mechanical stability to be obtained are obtained. commercially acceptable, which are characterized by depositing smaller amounts of zeolite (or smaller amounts of zeolite-silicate aggregates). Even when a small quantity of silicate is present, it has been found that the bentonite helps to counteract any tendency of reaction between zeolite and silicate to form a particle of a larger size than that in which zeolite normally occurs, thereby preventing or the deposition of zeolite or zeolite silicate particles on washed fabrics is reduced.

The compositions containing bentonite are also more easily dissolved and distributed in the washing water, and this too is obviously due to the presence of bentonite therein. Another advantage of the present invention is that when a small quantity or no silicate is used, compositions containing carbonate and / or bicarbonate do not require the presence of anti-gelling agents to prevent excessive thickening of the mixture. Such additives are generally not necessary when the main detergent salt in the detergent is a phosphate and when a small quantity or no carbonate and / or bicarbonate is present, but in the case of non-phosphate compositions which often contain considerable amounts of carbonate and / or or bicarbonate, it is decidedly advantageous to exclude anti-gelling agents, both with regard to the manufacturing process and from an economic point of view.

According to the prior art for detergent compositions, softening compositions and detergent plasticizers, various detergent compositions can be prepared which contain one or more of the substances zeolite, bentonite, silicate, phosphate, NTA, quaternary ammonium compounds (plasticizer) and other components, usually together with a synthetic synthetic but although the descriptions contain extensive listings (sometimes referred to as 1452 629 IÅV '"washing lists") of virtually all materials used for a particular purpose in the detergent and plasticizer compositions, they do not include clear descriptions or regulations regarding detergent compositions. the compositions according to the present invention and especially this applies to such compositions containing a small quantity or no soluble silicate. It is not apparent from the description that the importance of the bentonite containing a sufficient amount of "lubricating" water between its plates nor that the advantage of the combination of the bonding and dissolving effect attributable to the "hydration" is understood. Many of the "reference" compositions contain significant quantities of sodium sulfate, a filler, possibly to improve the physical properties of the particles in the product, but this is not necessary in preparing the compositions of the present invention. invention, which may therefore have higher levels of active components (including detergents).

The spray-dried bead material of the present invention, which is useful as a detergent or for the preparation of a finely divided, detergent, synthetic, nonionic, organic detergent composition, by adding a synthetic organic detergent to the bead material characterized in that it contains 5 - 60% by weight of water-softening aluminosilicate, 2 - 40% by weight of bentonite which acts as a binder for the spray-dried beads and contains sufficient water to facilitate the dispersion of the bentonite and thereby preferably prevent the deposition of aluminosilicate on washed material, 5 - 60 % by weight of water-soluble detergent salt or a mixture of such detergent salts, 0 to 30% by weight of water-soluble synthetic organic detergent and 0 to 5% by weight of water-soluble silicate, the content of water-soluble silicate being sufficiently low to prevent unacceptable deposition of zeolite. silicate 452 629 a 'w reaction product on washed laundry tgods. The detergent can be distinguished by the fact that it deposits smaller quantities of particles due to the presence of bentonite and a low content of water-soluble silicate or the absence of silicate in the spray-dried material. The aluminosilicate may consist of a zeolite with significant exchange capacity with respect to calcium ions, the bentonite has a significant swelling capacity in water and includes a sufficient quantity of water to facilitate the dissolution of the bonds between the bentonite plates when the detergent beads, alone or in admixture with others detergent components, are mixed with water, and the water-soluble detergent or mixture of detergents consists of polyphosphate, nitrile triacetate or carbonate, and no soluble silicate is present. The invention also relates to detergent compositions prepared by spray-drying the described bead composition with an anionic detergent present in the mixture, or by spraying a nonionic detergent in liquid form on drum detergent-free beads or on beads containing relatively small amounts. anionic detergent or mixtures of anionic detergents. Mixtures of the compositions, such as mixtures of anionic and nonionic detergent compositions, are also useful and may have superior washing properties.

The zeolites used include crystalline and amorphous zeolites and mixtures thereof, both of natural and synthetic origin, which can counteract the hardness due to calcium ions in the washing liquid sufficiently quickly and sufficiently effectively. Preferably, these materials are capable of reacting rapidly enough with the calcium ions so that they, alone or in conjunction with other water-softening compounds in the detergent, soften the wash liquor before adverse reactions between these ions and other components of the synthetic organic de - the tergent composition takes place. The zeolites used can be said to have a large ion exchange capacity relative to calcium ions, which is generally between about 200 and 400 milligram equivalents or more of the calcium carbonate hardness per gram of aluminosilicate, preferably 250 - 350 mg eq. / g.

Preferably they also have a softening rate with respect to residual hardness of 0.02 - 0.05 mg CaCO 3 / liter within 1 minute, preferably 0.02 - 0.03 mg / l, and less than 0.01 mg / l within 10 minutes. all based on anhydrous zeolite. Although other ion exchange zeolites may also be used, in the practice of the present invention the synthetic zeolite is generally used, in the form of finely divided detergent particles having the formula (Na 2 O) x - (Al 2 O 3) y - (sio 2) Zw H 2 O in which x is 1, y is between 0.8 and 1.2, preferably about 1, z is between 1, 5 and 3.5, preferably 2-3 or about 2, and w is between 0 and 9, preferably 2.5 - 6.

The zeolite should be a monovalent cation exchange zeolite, i.e. it should be an aluminosilicate with a monovalent cation such as sodium, potassium, lithium (whenever possible) or any other alkali metal, ammonium or hydrogen (in some cases). Preferably, the monovalent cation of the zeolite molecular sieve is an alkali metal cation, especially sodium or potassium and most preferably sodium.

Crystalline types of zeolite which, at least in part, are useful as good ion exchangers according to the invention include zeolites from the following crystal structure groups: A, X, Y, L, mordenite and erionite, and of these types A, X and Y are preferred. Mixtures of these molecular sieve zeolites may also be suitable, especially when A-type zeolite is present. These crystalline types of zeolites are well known in the art, and are described in more detail in the book Zeolite Molecular Sieves by Donald W. Breck, published 1974 by John Wiley & Sons. Typical commercially available zeolites of the mentioned structure types are listed in Table 9.6 on pages 747 - 749 of the said Breck. These zeolites are known in this technical field. Some suitable zeolites have been described in many patents in recent years as useful as detergent activators in detergent compositions.

The zeolite used according to the invention is generally synthetic, and it is often characterized in that it has a network of substantially uniform pores in the range of about 3 to 10 Angstroms, often about 4 Å (normally), the size of which is determined solely by the uniform the structure of the zeolite crystals. Preferably, this is of type A or similar structure as described in particular on page 133 of the said publication. Good results have been obtained when using a molecular sieve zeolite of type 4A, the monovalent cation of the zeolite being sodium and the pore size of the zeolite being about 4 Å, and these zeolites being preferred. The zeolite molecular sieves are described in U.S. Pat. No. 2,882,243 where they are designated Zeolite A.

Molecular sieve zeolites with ion exchange and water softening properties can be prepared either in a dehydrated or calcined form, containing between about 0 or about 1.5% to about 3% water, or in a hydrated or aqueous form containing bound water in an amount of from about 4% magnifying glass to about 36% of the total weight of the zeolite, depending on the type of zeolite used. The aqueous hydrated form of the molecular sieve zeolite (preferably hydrated to about 15-70% of its capacity) is preferred in the practice of the present invention when a crystalline product is to be used. The method of preparing the crystals is well known. For example, in the preparation of Zeolite A as above, the hydrated zeolite crystals formed in the crystallization medium (such as an aqueous amorphous sodium aluminosilicate gel) are used, without being subjected to a high temperature dehydration (calcination to 3% water content or less), which are normally carried out in the preparation of such crystals intended as catalysts, e.g. cracking catalysts.

The crystalline zeolite, either in fully hydrated form or in partially hydrated form, can be recovered by filtering the crystals from the crystallization medium and air drying at ambient temperature until the water content therein is in the range of about 5 ~ 30%, preferably about 10 or 15%. to 25%, such as 17-22%, e.g. 20%.

However, the moisture content of the molecular sieve zeolite used may be lower, as mentioned earlier, in which case the zeolite may be hydrated during mixing and other processing.

Preferably the zeolite should be in a finely divided form with a maximum particle diameter of up to 20 microns, e.g. 0.005 or 0.01 to 20 microns, more preferably between 0.01 and 15 microns, e.g. 3 - 12 microns, and in particular an average particle size of 0.01 - 8 microns is preferred, e.g. 3 - 7 microns, if crystalline, and 0.01 - 0.1 microns, e.g. 0.01 - 0.05 microns if it is amorphous. Although the final particle size is much smaller, the zeolite particles should generally have a size in the range of 100 - 400 mesh, preferably l40 - 325 mesh. Zeolites of smaller sizes often emit unpleasant dust and those of larger sizes cannot adequately and satisfactorily adhere to carbonate, bicarbonate, phosphate and / or NTA core particles on which they can be distributed together with the bentonite, such as in a gel-like or film-like conditions, during the spray-drying of a mixture for the production of bead material.

The bentonite used is a colloidal clay (aluminum silicate) containing montmorillonite. Montmorillonite is a hydrated aluminum silicate, in which about 1/6 of the aluminum atoms can be exchanged for magnesium atoms, and with which varying amounts of hydrogen, sodium, potassium, calcium, magnesium and other metals can be loosely combined. The type of bentonite clay most suitable in the preparation of the bead material of the invention is that designated sodium bentonite (or Wyoming or western bentonite) and which is normally a light to off-white soft powder, which in water forms a colloidal suspension with strong thixotropic characteristics. In water, the swelling capacity of the clay should generally be in the range 3 - 15 ml / gram, preferably 7 - 15 ml / g, and its viscosity at 6% concentration in water should generally be in the range 3 - 30 centipoise, preferably 8 - 30 cP. Preferred swellable bentonites of this type are sold under the Mineral Colloid brand, in the form of industrial bentonites, by Benton Clay Company, a subsidiary of Georgia Kaolin Co. These materials, which are the same as those previously sold under the Thixo-Jel brand, are selectively obtained and processed bentonites, and the ones considered most suitable are Mineral Colloid with No 101, etc. corresponding to Thixo-Jel with the numbers 1, 2, 3 and 4 These materials have a pH value (6% concentration in water) in the range 8 - 9.4, a maximum free moisture content of about 8% and a specific gravity of about 2.6, and in the case of the powdered quality passes about 85% through a 200 mesh screen according to the US screen series. Processed Wyoming bentonite is preferred as a component in the compositions in question, but other bentonites are also useful, especially if they form a minor part of the bentonite used. Although it is desirable to limit the maximum free water content, as mentioned, it is even more important to make sure that the bentonite used includes a sufficient amount of free water, most of which is assumed to occur between adjacent bentonite slabs, in order to facilitate rapid dissolution of the bentonite and any other materials in the particles, when these or the detergent compositions containing them are brought into contact with water, for example washing water. It has been found that at least about 2%, preferably at least 3% and in particular about 4% or more water should be present in the bentonite from the beginning before it is mixed with the other bead components in the mixer, and this content should also be present after spray drying. In other words, excessive drying to the point where the bentonite loses its "internal" moisture content can significantly reduce the usefulness of the compositions in question. When the moisture content of the bentonite is too low, the bentonite does not help to prevent the formation of silicate-zeolite agglomerates, nor does it help to facilitate the dissolution of the beads in the washing water. When the bentonite has a satisfactory moisture content, it has a content of exchangeable calcium oxide which is in the range of about 1 - 1.8%, and for magnesium oxide this content is normally in the range 0.04 - 0.41. A typical chemical analysis of the materials is 64.8 - 73.0% SiO 2, 1.4 - 1.8% Al 2 O 3, 1.6 - 2.7% MgO, 1.3 - 3.1% CaO 2, 2.3 - 3.4% Fe 2 O 3, 0.8 - 2.8% Na 2 O and 0.4 - 7.0% K 2 O.

The detergent salt used or mixtures thereof may consist of one or more of the materials conventionally used as detergents or which have been suggested as suitable for this purpose. They include both inorganic and organic detergents and mixtures thereof. Of the inorganic detergent salts, various phosphates, preferably polyphosphates, e.g. tripolyphosphates and pyrophosphates such as pentasodium tripolyphosphate and tetrasodium pyrophosphate. Trisodium nitrile triacetate (NTA), preferably in the form of the monohydrate, and other nitrile triacetates, such as disodium nitrile triacetate, are preferred water-soluble detergent salts. Sodium tripolyphosphate, sodium pyrophosphate and NTA can be used in hydrated forms, but even when anhydrous compounds are used, the bentonite and zeolite appear to prevent baking due to subsequent hydration. Carbonates, such as sodium carbonate, are of course useful detergent salts and they may be advantageously used alone or in combination with bicarbonates, such as sodium bicarbonate. When polyphosphates are used, it may be advantageous for sodium pyrophosphate to be present together with the sodium tripolyphosphate in a mutual ratio of between 1: 10 and 10: 1, preferably between 1: 5 and 5: 1, the total quantity of both of these detergent salts is about the same as indicated here for the sodium tripolyphosphate. Other water-soluble detergent active substances which are considered to be effective include various other inorganic and organic phosphates, borates e.g. borax, citrates, gluconates, EDTA ~ and iminodiacetates. Preferably the various detergent active substances should be in the form of the alkali metal salts, either the sodium or potassium salts or mixtures thereof, but in general the sodium salts are preferably used. In certain cases, such as when preparing neutral or slightly acidic detergent compositions, acidic forms of the detergent salts and in particular of the organic detergent active substances may be preferred, but in general the salts should be either neutral or basic. . Silicates and preferably sodium silicate with a Na 2 O: SiO 2 ratio in the range 1: 1.6 to 1: 3.0, preferably 1: 2 to 1: 2.8 e.g. 1: 2.35 or 1: 2.4, also function as detergent salts, but due to their strong binding ability and their ability to contribute to an aggregate v 1-. -s ......., -., ~ ...-....._........._.._....__....._ .. In a fermentation or agglomeration together with the zeolite particles, they constitute a special kind of detergent active substances, and preferably they should not be included in the compositions in question. However, since they have anti-corrosion properties, which is especially important when the detergent solution is to be used in washing machines or other devices in contact with their aluminum parts, in that case the hydrated sodium silicate particles may preferably be present in small quantities. are added afterwards so that they do not react with or agglomerate with the zeolite particles during mixing and spray drying. Although sodium sulphate and sodium chloride as well as other fillers do not have detergent activating properties, they are sometimes included in detergent compositions due to their properties as fillers. In addition to increasing the volume and weight of the product to facilitate dosing, they also in some cases improve the stability of the beads and the physical properties of the beaded detergent composition in which they are incorporated. Since the compositions in question are satisfactory without the presence of any fillers, they are preferably completely excluded, or their content is limited to a minimum, usually to a practical minimum.

In general, the detergent (s) used should be either nonionic or anionic or both, but amphoteric or ampholytic detergents may also be used, especially in conjunction with nonionic and / or anionic detergents in the compositions. Cationic detergents can act as plasticizers for fabrics in the products, but should not normally be spray dried together with anionic detergents due to an undesirable interaction that may occur. These types of substances are well known and have been described repeatedly in the detergent art. Since they are not preferred components in 452 629. nn the compositions in question, no reason is considered to exist for a further description of the same. Although various nonionic detergents with satisfactory physical properties can be used, including condensation products of ethylene oxide and propylene oxide with each other and with hydroxyl-containing bases, such as nonylphenol and the oxo type of alcohols, it is highly suitable that the nonionic detergent be a condensation product of ethylene oxide and higher fatty alcohol. In these 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. Most preferably, the nonionic The active detergent may be one in which the higher fatty alcohol has about 12 to 13 or 15 carbon atoms and which contains from 6 to 7 or 11 moles of ethylene oxide. Such detergents are manufactured by Shell Chemical Company and sold 23-6.5 and 25.7. One of their particularly appealing properties, apart from being good jes under the brand name Neodol detergents with regard to grease stains on materials to be washed, is that they have a comparatively low melting point, but still much higher than room temperature to be able to sprayed on the bead material in the form of a liquid which then solidifies.

Various anionic detergents, usually in the form of sodium salts, may be used, but the most preferred are linear higher alkyl benzene sulfonates, higher alkyl sulfates and higher fatty alcohol polyethoxylate sulfates. In the higher alkylbenzene sulfonate, the higher alkyl group is preferably straight and contains 12 to 15 carbon atoms, e.g. 13 carbon atoms, and it is a sodium salt. The alkyl sulphate is preferably a higher fatty alkyl sulphate having 10 to 18 carbon atoms, preferably 12 to 16 carbon atoms, e.g. 12 carbon atoms, and also this is added in the form of the sodium salt. The higher alkyl ethoxam sulphates should also have 10 or 12 to 18 carbon atoms, e.g. 12 carbon atoms, in the higher alkyl group, which is preferably a fatty alkyl, and the ethoxy content should generally be between 3 and 30 ethoxy groups per mole, preferably 3 or 5 to 20. Here again the sodium salts are preferred.

Thus, it appears that the alkyl groups are preferably straight with higher fatty alkyl groups containing 10 to 18 carbon atoms, the cation being preferably sodium, and when a polyethoxy chain is present the sulfate is present at the end thereof. Other suitable anionic detergents are the higher olefin sulfonates and the paraffin sulfonates, e.g. the sodium salts in which the olefin or paraffin groups have 10 to 18 carbon atoms. Particular examples of preferred detergents are sodium tridecylbenzenesulfonate, sodium tallow alcohol polyethoxy (3 EtO) sulfate and hydrogenated sodium tallow alcohol sulfate. In addition to the mentioned preferred anionic detergents, others from this well-known group may also be present, especially in only minor amounts relative to those previously described. Mixtures thereof may also be present, and in some cases such mixtures may be superior to the individual 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 and Berch, published in 1958 by Inter Science Publishers, Inc.

Various adjuvants may be present in the mixture from which the bead material or detergent compositions may be prepared by spray drying, or such adjuvants may be added afterwards, the manner of adding them often depending on the physical properties of the adjuvant, its heat resistance, its resistance to decomposes in the aqueous mixture and its volatility. One of the more important of these adjuvants is a polyacrylate, which has been found to be useful in regulating the properties and bulk volume of the beads, which has dispersing, anti-precipitating and anti-reprecipitating effects in the compositions in question and which contribute to keep the mixture liquid and homogeneous.

The polyacrylate present in the preferred bead material of the invention is a low molecular weight polyacrylate, and the molecular weight is usually in the range of about 1000 to 5000, preferably 1000 to 3000, and in particular 1000 to 2000 or about 2000. The polyacrylate may be partially or completely neutralized, e.g. 1/2 or 1/3 present in the form of sodium polyacrylate. Although modified polyacrylates may be substituted for the described sodium polyacrylate, including certain other alkali metal polyacrylates and hydroxylated polyacrylates, such yield should preferably be limited to a minor portion of the material, and most preferably the polyacrylate should be an unsubstituted sodium polyacrylate. Such materials are available from Alco Chemical Corporation under the trademark Alcosperse. The sodium polyacrylates are available in the form of clear amber liquids or powders, the solids content of the solutions being about 25 - 40%, e.g. 30%, and the pH value of the solutions, or of a 30% aqueous solution of the powder, is in the range of about 7.5 - 9.5, e.g. approx. 9. The materials are completely soluble in water and have been used as dispersants. They have been shown to bind calcium ions and have been used to prevent the precipitation of insoluble calcium compounds from aqueous solutions. In the spray-drying process in question, small quantities (or percentages) thereof contribute to improving the porosity of the resulting beads. When the mixture contains carbonate and / or bicarbonate and silicate, and although the amount of silicate is small, there may be a tendency for the mixture to gel or "solidify" in the mixer, especially if the mixture is due to If silicate is present, process aids are also preferably present in the mixture (and consequently in the finished bead material and in the detergent composition) in order to prevent premature solidification or These preferably consist of citric acid and magnesium sulphate, instead of citric acid one can use soluble citrates, such as sodium citrate, and although anhydrous magnesium sulphate is preferred, various hydrates thereof can be used, such as epsom salts. In exchange for the preferred anti-gelling system, other adjuvants and suitable systems may be added to keep the mixture in liquid form, such as sodium sesquicarbonate, which is added instead of a portion of the sodium carbonate and sodium bicarbonate. Although the processing aids are useful in many cases, it is a feature of the present invention that they are not necessary in the preparation of the preferred bead material from which silicate is excluded. Although certain adjuvants, such as fluorescent whitening agents, pigments e.g. ultramarine blue, titanium dioxide and an inorganic filler in the form of a salt can be added to the mixture, then other adjuvants such as perfumes, enzymes, bleaches, certain dyes, bactericides, fungicides, fabric softeners and flow improvers can often be sprayed on or on otherwise mixed with the bead material or the spray-dried detergent composition, together with any nonionic detergent and / or separately, so as not to be adversely affected by the elevated temperatures during the spray-drying, and also for the presence of the same in the spray-dried bead material should not inhibit the absorption of nonionic detergent when it is subsequently sprayed on the beads. In the case of stable and normally solid adjuvants, however, it is possible to mix these from the beginning into the slurry in the mixer. It is thus conceivable that pigments and fluorescent whitening agents, when used, are normally included in the mixture from which the bead material in question is prepared by spray drying.

The preferred dye is ultramarine blue, but other stable pigments and dyes may be used in conjunction with this or instead of the same. Since the spray-dried bead material according to the invention can sometimes be discolored, usually due to the use of naturally occurring minerals, the color shift from the dye can be adversely affected. It has been found that the incorporation of a small quantity of titanium dioxide into the mixture helps to retain the desired color tone from the dye, and the presence of titanium dioxide does not appear to have a negative effect on the appearance of laundry washed with detergent compositions prepared. of bead material containing the same.

Of the fluorescent whitening agents, Tinopal SBM is the most preferred, especially in extra concentrated form. However, various other whitening agents for cotton may be used, such as those sometimes referred to as CC / DAS whitening agents, derived from the reaction product of cyanuric chloride and the disodium salt of diaminostilbene disulfonic acid, including variations thereof with respect to the substituents on the triazine and aromatic rings. This class of bleach is known in the detergent field and is commonly used when bleaching components are not included in the final product. When it is desired to include bleaching agents in the detergent composition, such as sodium perborate or other oxidizing bleaching agents, bleaching stable whitening agents should generally be incorporated into the mixture. These include the benzidine sulfonic disulfonic acids, the naphthotriazolyl-stilbenzulfonic acids and benzimidazolyl derivatives. Polyamide whitening agents which may also be included include aminocoumarin or diphenylpyrazoline derivatives, and polyester whitening agents which may also be included include naphthotriazolyl stilbenes. These whiteners are normally used in the form of the soluble salts, but they can also be used in the form of the corresponding acids. Cotton bleaches generally make up the largest part of the bleach systems used.

The enzyme preparation that is normally added to the bead material afterwards due to its heat sensitivity can be any variant of the commercially available products, among which may be mentioned Alcalase, manufactured by Novo Industri, A / S, and Maxatase , both of which are alkaline proteases (subtilisin). Maxazyme 375 is sometimes preferred. Although the alkaline proteases are the most widely used, amylotic enzymes, such as alpha-amylase, can also be used. The compositions mentioned generally contain active enzymes in combination with an inert powdered vehicle, such as sodium or calcium sulphate, and the content of active enzyme can vary widely, generally being between 2 and 80% in the commercial product. In this description, the stated quantities refer to the enzyme preparations and not only the active part therein. The perfumes used, which are usually heat sensitive and may include a solvent such as alcohol, usually consist of synthetic perfume materials, sometimes in admixture with natural components, and generally contain alcohols, aldehydes, terpenes, fixatives and other perfume normal components. . Agents favorable for flowability, such as special clays which are sometimes added to detergent products because they often improve the flowability of and reduce the adhesion of various compositions, are in this case unnecessary, possibly partly dependent on on the presence of bentonite and the absence or very limited presence of silicate. However, they can be added, if desired, to further increase the flowability. Although it has been found that detergent compositions prepared from the bead material in question do not require the presence of any anti-corrosion additive to replace the omitted silicate, suitable such materials may be used according to the invention, and preferably those which are stable in mixing. and spray-drying conditions, and which do not adversely affect these work stages. The anti-corrosion additives or antioxidants may be organic or inorganic, with inorganic materials generally being preferred, and preferably those which are suitable for preventing corrosion on the aluminum parts of the washing machine are selected. If it is desired to continue using silicate for this purpose or to insert silicate due to its effect on hardness caused by magnesium ions, a powdered silicate, such as anhydrous sodium silicate, which is commercially available under the trademark Britesil and is manufactured, is generally preferred. of Philadelphia I Quartz co (Na2o = sio2 = 1 = z, 4), and this is preferably added afterwards. Other normally solid soluble silicates, preferably of alkali metals, can also be added afterwards to the bead material according to the invention, preferably after any absorption of nonionic detergent has been carried out.

If it is desired that the product produced should have the ability to make the laundry softer, plasticizers, preferably in the form of dry powder, can also be added to the bead material in a suitable manner afterwards. This class of material is well known, and very often the plasticizers are cationic compounds, especially quaternary ammonium compounds. Such as quaternary ammonium halides. Particularly preferred are the higher alkyl, alkylaryl and arylalkyl lower alkyl quaternary ammonium chlorides and bromides, such as distearyl dimethylammonium chloride. Of the commercial plasticizers, the most preferred are those sold under the trademark Arosurf TA-100, manufactured by Sherex Chemical Company, Inc. These compounds also have antistatic and antibacterial properties, but if desired, other antibacterial adjuvants may also be used, which are - preferably the product is added afterwards.

Of course, water is present in the mixture to act as a dispersing medium for the various other components of the bead material, and some water in both free form and hydrate form is present in the product. During the drying of the bead material, the water content therein, which should initially be about 25 - 60%, can be reduced to about 5 - 15%, the water content having to be sufficient for the bentonite in the dried beads to have a water content of at least 2% and preferably at least 4%. Preferably, deionized water is used, so that the content of hard ions therein can be very low and so that the amount of metal ions which can cause decomposition of any organic materials which may be present in the mixture, the bead material and the detergent is reduced to a minimum, but city water or tap water can usually be used instead.

Normally the hardness of the water should be less than 150 ppm, such as CaCO 3, and preferably the hardness should be less than 100 ppm and most preferably less than 50 ppm.

The contents of the various components of the bead material and of the bead spray-dried detergent composition should be such that they become free-flowing and, in the case of the bead carrier material, it can sufficiently absorb a nonionic detergent which in liquid form. applied thereto and thereby provides detergent compositions which are sufficiently free-flowing. The detergent compositions should, of course, also be effective detergents in which the detergent salts are present to support the organic detergent with respect to its cleaning effect in aqueous solutions of the compositions, and it is important that the resulting products be such as not to cause unwanted deposits of zeolite particles (or zeolite-silicate aggregates) on washed materials. Although insoluble, the zeolite particles and bentonite particles do not cause unsatisfactory discoloration or light discoloration of the laundry because they have a small particle size, but such discoloration may occur when zeolite aggregates are formed which are large enough to be retained by the fabrics. and can also be easily distinguished with the naked eye, especially when significant quantities thereof are not removed from washed materials by blowing them away with the drying air during automatic drying. It is also desirable that the bead material produced and the detergent composition in the form of beads have a suitable bulk volume and color. It has been found that satisfactory bead material which satisfies the mentioned requirements consists of 5 - 60% by weight of water-softening aluminum silicate (zeolite), 2 - 40% by weight of bentonite (with the desired moisture content) and 5 - 60% by weight of water. soluble detergent or mixture of such substances. Between 0 and 30% by weight of water-soluble synthetic organic detergent and / or between 0 and 5% by weight of water-soluble silicate may also be present, but often these are preferably not included. The spray-dried beads should preferably contain 3 to 15% by weight of water and more preferably 5 to 12% by weight of water and generally between 7 and 10% by weight of water, including any hydrated water present. The hydride can be present in the zeolite, NTA, phosphate, carbonate, bicarbonate and magnesium sulphate, when these are included in the composition, in addition to that present between the bentonite plates. The stated water content also includes tightly bound hydrate water, such as that still retained by zeolite even after several hours of distillation of a toluene dispersion. In some cases, such as when the concentration of zeolite in the product is high, so that up to about 12 to 15% by weight of water may be present in the zeolite such as hydrate water, the water content of the spray dried beads may be as high as 20% by weight, and occasionally it amounts to about 25% by weight.

However, in order to obtain good flowability of the product and to reduce stickiness and agglomeration to a minimum, the upper limit should generally be about 15% by weight, especially when the final detergent composition contains a considerable quantity of nonionic detergent. The given percentage of zeolite includes the hydrate water therein. It is possible to produce useful spray-dried beads with a moisture content of less than 3% by weight, provided that a sufficient amount of water is taken up in the bentonite, due to the foregoing reasons, but because the zeolite has a great ability to attract water and due to of the behavior of the other hydratable materials that may be present, it has generally been found that at least 3% by weight of water is required to avoid loss of the desired internal water content of the bentonite, which water appears to "lubricate" the plates and facilitate their separation when product containing the same is dispersed in water. When anhydrous products are produced, and even when a sufficient amount of water is retained in the bentonite, they tend to be physically unstable, to pulverize more easily and to be subject to abrasion and decomposition. 10 15 20 25 30 35 452 629.

'I' 23 The bulk volume of the spray-dried beads can be in the range 0.2 - 0.9 g / cc. Bulk volumes within the lower part of this range can be more easily obtained when no silicate is present in the mixture to be spray-dried and when a small quantity or no non-active detergent is absorbed by the beads. The higher bulk volumes are obtained when nonionic detergent is applied to porous beads and when some silicate is present in the beads. The lighter products have bulk volumes in the range 0.2 - 0.5 g / cc, often 0.3 - 0.4 g / cc, and the heavier particles have bulk volumes in the range 0.6 - 0.9 g / cc, usually 0.6 - 0.8 g / cc. The particle size of the beads should generally be in the range of 10 to 100 (through No. 10 and at No. 100) according to the US screen series, preferably 10 to 60 according to the US screen series. In preferred compositions, the ratio of bentonite to zeolite is in the range of 1: 4 to 1: 1, the ratio of water-soluble detergent to zeolite is in the range of 1: 2 to 3: 1, and the ratio of bentonite to water-soluble detergent substance is in the range l: l0 to lzl. More preferred ranges for these ratios are 1: 3 to 2: 3, 2: 3 to 2: 1 and 1: 6 to 1: 2, respectively. In percentage terms, the compositions preferably contain 10 to 40% of partially hydrated sodium zeolite, preferably containing 15 to 25%. % by weight of hydrated water and having a calcium ion exchange capacity in the range of 200 to 400 milligram equivalents of calcium carbonate hardness per gram of anhydrous zeolite, 2 to 35% bentonite of a type having a swelling capacity in the range of 7 to 15 ml / g and having a viscosity in the range 8 - 30 cP at 6% concentration in water, 10 ~ 50% water-soluble detergent alkali metal salt or a mixture thereof, 0 - 35% water-soluble synthetic anionic organic detergent and 0 - 3% water-soluble silicate, which silicate when present is an alkali metal silicate having an alkali metal oxide: silica ratio in the range of 1: 1, 6 to 1: 3, and preferably 1: 2 to 10 15 25 25 452 629 then 24 1: 2, 8. The even more preferred bead compositions contain 15 - 35% zeolite A, 5 - 20% processed Wyoming bentonite, 20 - 50% water soluble detergent sodium salt or mixtures thereof, 0 - 20% water soluble synthetic anionic organic detergent and 0% sodium silicate. Although detergent carbonates and bicarbonates are useful in the preparation of the bead material of the invention, particularly those to be sprayed with nonionic active detergent, detergent polyphosphates and / or nitrile triacetates are often preferred in the spray dried beads, although these include anionic detergent or not, and whether or not nonionic detergent should be applied to them. Preferred pearl compositions based on NTA as the sole or major soluble detergent substance contain 15-35 or 40% hydrated zeolite, 5 or 10 to 20% bentonite and 20 to 50 or 60% NTA.

When a phosphate, such as sodium tripolyphosphate, is to be the main or substantially water-soluble detergent salt, the same proportions of zeolite and bentonite may be used, but in general more phosphate may be present '(than NTA). In the case of such bead material on which nonionic detergent is to be sprayed, or comparable compositions based on carbonate or a mixture of bicarbonate and carbonate (with the ratio of carbonate bicarbonate in the spray-dried bead material in the range of about 1 to 3), preferably no water-soluble synthetic organic detergent and only a small quantity or no soluble silicate are present. When bicarbonate and carbonate together are included in the compositions, they should generally constitute 20 - 40% of the bead material, and when only carbonate is included, this should usually constitute 10 - 30% thereof. When an anionic detergent or other suitable organic detergent is included in the mixture to give a spray dried detergent product, the preferred levels thereof should be 3 or 5 to 30%. , even more preferably 5 - 25% and in particular 10 - 25%, e.g. 10%, 15% of the product, and the detergent should preferably be selected from the group consisting of linear sodium alkyl benzene sulfonate in which the alkyl group has 10 to 18 carbon atoms, sodium fatty alcohol sulfate in which the alcohol group has 10 to 18 carbon atoms and sodium fatty alcohol ethoxylate sulfate in which the fatty alcohol group has 10 - 18 carbon atoms and containing between 3 and 30 ethylene oxide groups per mole, and mixtures thereof.

At present, linear sodium tridecylbenzenesulfonate is most preferred, and the alkyl groups preferably have 12 to 16 carbon atoms.

When a nonionic detergent is absorbed into the spray-dried base beads (and in some cases a small quantity may be absorbed into the spray-dried detergent beads), its content should generally be in the range of 5 or 8 to 30%, preferably 10-25%, t. ex. 15%, 20%. In this case, the preferred nonionic detergent is a condensation product of 6 to 12 moles of ethylene oxide and 1 mole of a higher fatty alcohol having 12 to 16 carbon atoms.

When polyacrylate is present in any of the detergent compositions or in the carrier material in the form of beads, this should normally be between 0.05 and 1% thereof, and its molecular weight is preferably in the range 1000 - 5000.

Since the presence of anionic detergent in the spray-dried detergent beads can counteract the production of a bead structure capable of absorbing a desired quantity of nonionic detergent, it may be advantageous to produce spray-dried detergent beads of a type according to the invention. 452 629 al. The mixture and mix these with base beads according to the invention which have been sprayed with nonionic detergent, so that larger quantities of nonionic detergent can be present in the final product. When this happens, varying areas for the concentrations can be used, 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. It is desirable that the bulk volumes of the beads prior to mixing be approximately the same, preferably within 0.1 g / cc relative to each other, and the particle sizes should be approximately the same, generally within the No. 10-100 range of U.S. Pat. sieve series, to prevent sieving and separation of the final mixture.

The levels of adjuvants and processing aids in the base beads and the spray-dried detergent should generally be limited to 20% thereof, and preferably 1 to 10% and in particular 3 to 7% thereof. The levels of process aids, when magnesium sulphate and citric acid are used, should generally be 0.5 - 2% magnesium sulphate, preferably 1-1.5% thereof, and 0.1 - 0.5% sodium citrate, preferably 0.1 - N ' 0.3% thereof. In the case of dyes, pigments and fluorescent whitening agents, when present, their levels should generally be 0,05 - 0,6% of color pigments, such as ultramarine blue, preferably 0,2 - 0,4%, and 0, 1 - 4% fluorescent bleach, preferably 1 - 3% thereof. The content of titanium dioxide (a white pigment) should generally be 1 - 3%, preferably 1 - 5 - 2.5%. If a dye or dyes is used instead of a color pigment, its content should generally be 1 - 50% and in particular 5 - 20% of the quantity of color pigments.

In the preferred spray-dried bead material of the present invention, which may contain NTA or polyphosphate as detergent active agents together with or 10 15 25 452 629 u å. 27 without synthetic organic detergent, or which may contain such detergent together with any of the previously listed preferred water-soluble detergent salts, the bulk volume is in the range 0.2 - 0.8 g / cc, the aluminum silicate is hydrated zeolite A, the bentonite includes at least 3% water, based on anhydrous bentonite, the water-soluble silicate, if present, is sodium silicate with Na 2 O: SiO 2 ratio in the range 1: 2 to 1: 2.8, and the water content of the beads is between 3 and 12 % thereof. When the beads contain NTA or some other salt of nitrile triacetic acid, together with or without synthetic organic detergent, the bentonite: zeolite ratio is in the range 1: 6 to 1: 2, the NTA: zeolite ratio is in the range 1: 2 to 2: 1 and bentonite: the NTA ratio is in the range 1: 6 to 1: 2, and the percentages of hydrated zeolite, bentonite, sodium nitrile triacetate and silicate are in the range 10 - 40%, 2 - 25%, 10 - 40 % and 0 - 5% respectively.

When the preferred NTA-containing beads also contain a synthetic anionic organic detergent, together with the aforementioned zeolite A, bentonite and water, and together with or without soluble silicate, they preferably contain 5 to 30% synthetic anionic organic detergent, which may consist of linear sodium alkylbenzene sulfonate wherein the alkyl group has 10 to 18 carbon atoms, sodium fatty alcohol sulfate wherein the alcohol group has 10 to 18 carbon atoms or sodium fatty alcohol ethoxylate sulfate wherein the fatty alcohol group has 10 to 18 carbon atoms and which contains 3 to 30 ethylene oxide groups per mole or a mixture of two or several of these, the water-soluble detergent is a sodium salt of nitrile triacetic acid (NTA), the bentonite zeolite ratio is in the range 1: 6 to 1: 1, the NTA: zeolite ratio is in the range 1: 3 to 3: 1, bentonite: NTA the ratio is in the range of 1: 10 to 1: 1 and the ratio of synthetic anionic organic detergent ntzzeolite is in the range 1: 1 to 1: 4, and the percentages of hydrated zeolite, bentonite, sodium nitrile triacetate, synthetic anionic organic detergent and silicate are in the range of 10 - 40%, 2 - 25%, 10 - 40%, 10 - 25% (more preferred area) and 0 - 5% respectively.

For phosphate-containing beads, with or without synthetic detergent, the materials and conditions are the same as for the corresponding NTA-containing beads, with pentasodium tri-polyphosphate or tetrasodium pyrophosphate or mixtures thereof being included instead of NTA, but the percentages are here in the range 15 - %, 5 - 20%, 15 - 40% and 0 - 5% respectively. Similarly, in the case of phosphate-containing beads in which anionic detergent is also present, the material and conditions are the same as for the corresponding NTA-containing beads, and the percentage ranges are the same with the exception of the range of the total amount of polyphosphate, which is 10 - 50%.

The ranges of the contents of the various bead components in the final detergent composition, when the nonionic detergent is added afterwards, can be easily calculated from the contents (possibly together with other materials) given for the base beads minus the levels of detergent and other materials subsequently added. added to the beads. On the other hand, the contents of the bead components (and thereby the composition of the mixture) can be calculated on the basis of the composition of the final product. For example, when calculating the areas of the components of the final product based on the areas of the contents of the bead material, if only the nonionic detergent is added to the final detergent composition, so that the final product contains 20% nonionic detergent, starting from the different ranges given for the components of the bead material, calculate the ranges of the contents thereof in the final detergent composition by multiplying by 0.8, i.e. (100 - 20) / 100. Similarly, when the content of nonionic detergent (in the compositions where this is the only additive in the beads) can vary between 8 and 25% of the detergent composition, the multiplier should be between 0.92 and 0.75. The final percentage of nonionic detergent in the product should be in the range 8 - 30%, preferably 10 - 25% and in particular 15 - 22%, e.g. about 20%, but in some cases concentrations in the range 8 - 13% may be preferable for certain types of products. Usually the percentage of perfume in the final product should be in the range 0.1 - 1%, preferably 0.2 - 0.4%, the percentage of enzyme should be 0.5 - 3%, preferably 1 - 2%, and if anhydrous sodium silicate should be If added afterwards, its content should generally not be less than 1% and preferably be limited to about 5%, although in some cases as much as 10% has been used. When a plasticizer is present in the final product, its content should generally be in the range 3 - 12%, preferably 5 - 10%. The base beads and the spray-dried detergent beads according to the invention are spray-dried starting from an aqueous mixture, which should generally contain from about 40 to about 70 or 75% solids, preferably 50-65% thereof, the remainder being water. preferably deionized water, as mentioned earlier (but city water can also be used). The mixture is preferably effected by successively adding the various components therein in a manner which results in a highly miscible, easily pumpable and non-solidifying slurry intended for spray drying. The order in which the various components are added may vary, depending on the circumstances, but it is highly desirable that silicate in the solution (if any) be added last, and if not least at least after the addition of any gel- or "solidification" -previous combination of materials or process aids, such as citric acid and magnesium sulphate.Generally, it is preferred that all or almost all of the water be added to the mixer first, preferably at the working temperature, after which process aids (if any) and other secondary components, including pigments, and fluorescent whitening agents and polyacrylates, if any, are added followed by zeolite, water-soluble detergent, anionic detergent (if any), bentonite and silicate (if any) In general, in the additives each component must be thoroughly mixed before the addition of the next component, but the additive methods may vary depending on the circumstances, so that simultaneous additives can be allowed when appropriate. In some cases, the addition of a component may be divided into two or more parts, and sometimes different components may be mixed together before the addition to accelerate the mixing process. Normally, the mixing speed and ability increase as the material is added. For example, low speeds can be used until the last of the zeolite or soluble detergent is mixed in, after which the speed can be increased to medium speed and then to high speed, and this speed should preferably be maintained before, during and after the addition of any silicate solution. .

The temperature of the aqueous medium in the mixer should generally be about room temperature or elevated temperature, generally within the range of 20 - ao ° C, preferably 30 - 75 or 80 ° C and in particular 40 - 70 ° C. Heating the medium in the mixer can promote the dissolution of the water-soluble salts in the mixture and thereby increase the miscibility, but the heating if it takes place in the mixer can reduce the production rate and sometimes favor the solidification of the mixture. 10 15 20 25 30 452 629 s -w 31 An advantage of having process aids present in the mixture (especially when some soluble silicate is present) is that these guarantee that non-gelling slurries are obtained both at lower and higher temperatures. . Temperatures higher than 8000 (and sometimes higher than 70 ° C) should generally be avoided due to the possibility of decomposition of one or more of the components in the mixture, e.g. the sodium bicarbonate. In some cases, even lower temperatures in the mixer also raise the upper limits of the solids content of the mixture, probably due to insolubilization of normally gelling or solidifying components.

Mixing times to obtain good slurries can vary widely, from as little as 5 minutes in small mixers and for slurries with higher water contents, to as much as 4 hours in some cases. The mixing time required for mixing all components of the mixture into a substantially homogeneous medium can be as short as 10 minutes, but in some cases up to 1 hour is required, although 30 minutes is the preferred upper limit. Including any such initial mixing time, the periods in the mixer should generally be between 15 minutes and 2 hours, e.g. 20 minutes to 1 hour, but the mixture should be mobile, non-gelled or solidified, for at least 1 hour, preferably 2 hours and more preferably for 4 hours or longer, after completion of the preparation of the mixture, and preferably it should be mobile for as long as l0 - 30 hours before it is pumped out to the spray tower to provide opportunities for situations that involve encountering other manufacturing problems.

The slurry in the mixer, with the various salts and the other components dissolved or evenly distributed therein therein, is transferred in the usual manner to a spray tower, which is generally located near the mixer. The slurry is allowed to fall down from the bottom of the mixer to a feed pump, which at high pressure presses the mixture through spray nozzles at the upper end of a conventional spray tower (co- or countercurrent), in which the droplets of the slurry fall down through a hot drying gas, generally consisting of combustion products of heating oil or natural gas, the droplets being dried to the desired absorbent material in the form of beads. During drying, some of the bicarbonate (if any) can be converted to carbonate while releasing carbon dioxide which, in conjunction with any polyacrylate present in the mixture being spray-dried, improves the physical properties of the beads produced, so that they better absorb liquids, such as liquid nonionic detergent, which are then subsequently sprayed on them. However, the zeolite and bentonite components as well as the polyphosphate component (if any) in the bead material produced also appear to have a beneficial effect on the absorption of liquid and the production of a stable bead material, and the polyacrylate improves the beads properties and contributes to faster drying capacity. .

After drying, the products are sieved to the desired size, e.g. 10 to 60 or 100 according to the US screen series, and are then ready to be sprayed with nonionic detergent, if it is a composition which gives base beads, the bead material being either hot or cooled (to room temperature).

However, the nonionic detergent should generally have an elevated temperature, such as 30-60 ° C e.g. SOOC, to ensure that it has a liquid form; after cooling to room temperature, however, it is desirable that it be a solid, often wax-like substance. Although the nonionic detergent at room temperature is somewhat tacky, it does not cause the free flowing ability of the final product to deteriorate as the detergent penetrates below the bead surface or into the beads. The nonionic detergent which is applied in a known manner to moving or tumbling beads in the form of a spray mist or as droplets is preferably a condensation product of ethylene oxide and a higher fatty alcohol, as previously described, but other nonionic substances are also useful. . The enzyme material (hereinafter referred to as the enzymes, although it also includes a carrier), aqueous silicate and other powdered adjuvants may be powdered on the detergent particles, and perfume and other liquids added afterwards may be sprayed thereon at any convenient time, before or after addition (s). of the powder (s).

The spray-dried detergent, the spray-dried base beads and the detergent compositions prepared therefrom include a small quantity or no silicate resulting from the mixture, although some solid silicate may be added afterwards. The subsequently added powdered silicate, if present, does not appear to react with the zeolite as much, so the amount of zeolite-silicate agglomerates which tend to deposit on washed articles is reduced, compared with the amount of such deposited material derived from products in which the silicate has already been mixed into the mixer. Although silicate, even when bentonite is not present, is generally used due to its bead-moderating and anti-corrosion effects, the detergent compositions in question produce acceptable beads, and they have not been shown to cause corrosion on aluminum parts. Furthermore, the bentonite does not have a negative impact on the stability of the product, but in fact seems to help hold the beads together and make them resistant to crushing and pulverization during transport and use. The presence of bentonite markedly improves the properties of the final detergent composition 4:12 629 34 which results in greater binding rates with respect to the calcium ions and in the fact that less zeolite is deposited on washed fabrics. When low molecular weight polyacrylate is present, the beads become more porous and better absorb the nonionic detergent in liquid form, without excessively reducing the bulk volume of the product. Given that bentonite is a clay and serves as a binder, it can be expected that it in itself gives rise to deposition and gelation problems. The reduction of deposited quantities, the absence of gelation and the rapid dispersion are therefore surprising and constitute important results of the present invention. What must also be considered important results of the presence of the small quantity of polyacrylate in the spray-dried beads is the improved spray-drying of the base beads and detergent compositions of the invention and the improved sorption of liquid nonionic detergent by the base beads.

The following examples illustrate but do not limit the invention.

Unless otherwise stated, all temperatures refer to OC, and all parts in the examples and in the description refer to parts by weight. When the weights and contents of zeolite are stated, these refer to the use of the ordinary hydrate, since the hydrate water of the zeolite probably does not leave the zeolite and does not become part of the aqueous solvent medium in the mixing processes in question. Some of the water present in the bead material and detergent compositions is also present in the form of the hydrated water of the zeolite. Nor can the water contained in the bentonite be considered as free water, but due to the small percentage present, this difference can often be neglected for practical reasons. Example 1 (Comparative Example) 100 parts of a mixture intended for spray-drying into base beads, suitable for later conversion to a detergent composition by adding thereto a synthetic nonionic active organic detergent, was prepared by introducing 47 parts of deionized water with a temperature of about 27 ° C into the mixer, and then mixing at a low mixing speed from the beginning and 1.04 parts of Tinopal SBM Extra Conc. (CIBA-Geigy) f 0.13 parts ultramarine blue powder, 0.07 parts sodium polyacrylate (Alcosperse 107D), 21.11 parts Linde hydrated zeolite 4A (20% crystal water), 6.25 parts Mineral Colloid No 1 (bentonite ), 15.75 parts of sodium bicarbonate (industrial grade), 7.74 parts of sodium carbonate (natural calcined 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 speed, and after adding all the ingredients, which took about 15 minutes, the mixing was allowed to continue for about 1 hour (in some cases the mixing time can be as long as 4 hours ), during which time some of the water present, e.g. about 2 - 6 parts could disappear by evaporation and could be supplemented if desired. During the mixing time, the mixture was kept in continuous motion and neither gelled, solidified nor baked. Since the bicarbonate was partially decomposed into carbonate during spray drying, the quantities of bicarbonate and carbonate in the mixture can be varied depending on the properties of the spray tower.7 Starting 5 minutes after all components were added to the mixture, it was caused to fall from the mixer to a pump , which at a pressure of about Z1 kg / cm2 pumped it to the top of a countercurrent spray tower, in which the initial temperature was about 430 ° C and the final temperature was 1510 ° C. The substantially inorganic bead material obtained had a bulk volume of about 0.6 - 0.7 g / cc, an initial adhesion less than 10%, a particle size in the range mainly between 10 and 60 mesh according to the US screen series (they were screened for this size) and a characteristic fineness (through U.S. sieve No. 50) of about 15%. The moisture content of the beads was in the range 1 - 10%, and was normally closer to 10%, e.g. 8 - 10%. The base beads were found to be free-floating (80% buoyancy), non-sticky, sufficiently porous but still hard on the surface. They were able to easily absorb considerable quantities of liquid nonionic detergent without becoming impermissibly sticky.

Detergent products were prepared from the spray-dried beads by spraying a normally waxy nonionic detergent on the surface of the tumbling beads. Neodol 23-6.5 is used but Neodol 23-7 or Neodol 25-7 (and in some cases Neodol 45-II) can be used instead. The nonionic detergent was used in a heated liquid state (with a temperature of about 45 ° C). The quantity injected was such that a final product was obtained which contained about 20% of nonionic detergent. Proteolytic enzyme (Alcalase 1,7T or Maxazyme 375) was applied in powder form to a concentration of about 1.5% in the product, and perfume was sprayed on the product to a concentration of 0.25% therein. The resulting detergent compositions had a bulk volume of about 0.7 - 0.8 g / ml and contained about 32.45% zeolite (hydrated), 19.7% nonionic detergent, 18.5% sodium carbonate (of which a part formed by decomposition of the sodium bicarbonate), 1.3% sodium bicarbonate, 1.3% free water, 1.4% enzymes, 1.6% fluorescent bleach, 0.25% perfume, 0.2% ultramarine blue, 9, 6% bentonite, 0.1% sodium polyacrylate and 1.4% titanium dioxide.

The detergent prepared with the above composition 10 15 20 25 30 452 629 - v -fi 37 is an excellent very effective laundry detergent, especially suitable for washing household laundry in automatic washing machines. Its physical and aesthetic properties are appealing and advantageous, as it does not dust and is extremely free-flowing, which means that it can be packaged in narrow-necked glass and plastic bottles, from which it easily flows out during dosing. The prepared detergent compositions containing bentonite have, as described, improved calcium ion binding rates, but what is even more important is that they leave less residue on laundry washed therewith (in an automatic washing machine at general product concentrations and at normal washing temperatures), in particular. when the laundry is dried on a clothesline, than is the case with similar compositions containing less bentonite and in which sodium silicate is included in the spray-dried base beads. This difference is accentuated when the washing water has a high hardness, e.g. 200 ppm, as calcium carbonate, the wash water is cold and stirring is done gently.

The base beads and detergent composition as above are acceptable standard types with which other bead materials and detergent compositions described in the following examples can be compared and with which they can well withstand a comparison. Furthermore, the production methods are essentially the same and they can be considered acceptable.

During normal operation, the mixtures must be prepared quickly and can be taken out of the mixer just as quickly, sometimes being prepared in as short a period as 5 minutes and pumped out of the mixer in as short a time as 10 minutes.

However, it is often important that the mixtures in question can withstand at least 1 hour in the mixer without gelation or solidification, since such long delays can sometimes be expected in commercial production. The mixture described can be retained for as long as 4 hours, and often considerably longer, without gelling or solidifying, which is at least partly attributed to the content of bentonite and the absence of silicate. This effect of the bentonite is unexpected because the bentonite also has a thickening effect on the mixture in the mixer, but even though this mixture can thicken considerably, it still remains pumpable. Other minor components of the mixture, such as fluorescent whitening agents and pigments, may be excluded therefrom and enzymes and perfumes may be excluded from the final product, although it is highly desirable that all of these materials be present. The temperature of the mixture in the mixer can be modified, such as by raising to 5200, and the quantities of the various components can vary by 100%, 120% and 130% and still be kept within the above limits, while it is possible to obtain bear pickable mixtures which give the desired bead material and the desired detergent compositions. The content of solids in the mixture can vary within the given range, e.g. 45% and 65%, whereby good mixing and spray drying is obtained. The order may be different when loading the components in the mixer, but in general it is desirable that any silicate is added last or near the end, and preferably the bentonite should also be added late in the loading, preferably just before the silicate. Instead of Zeolite 4A, Zeolites X and Y can be used, as well as other types of Zeolite A. Although in this example it is preferred to use the about 80% hydrated zeolite 4A (about 20% water content), different degrees of hydration of zeolite acceptable, and in some cases almost anhydrous crystalline zeolites or amorphous zeolites may be used. A variation of the content of bentonite within the given range, to e.g. 7%, 13% or 19% in the base beads, still yield useful products, but those containing the larger amounts of bentonite are usually more effective in preventing 10 15 20 25 30 452 629. .

'I' 39 deposition of zeolite on the laundry. In some cases, it may be desirable to insert even higher percentages of bentonite, within the limits given in the description, care being taken that the other components of the base beads are such that the beads become free-flowing and effective detergents. The commercially suitable quantity of bentonite depends on a number of factors and is often a balance between the desired reduction of zeolite residues and the desired washing activity as well as other functional effects of other components in the detergent composition which may be included instead of an increased amount of bentonite.

The noted improvement of the detergent compositions according to this example which means that less residue is deposited on the laundry has been verified by testing the described product in comparison with a control product with essentially the same composition, but without the presence of bentonite and with a content of about 8% sodium silicate in the final product. In this comparison experiment a Whirlpool Suds Saver Model washing machine was used and the washing periods were every 8 minutes on a gentle washing cycle. The concentration of detergent composition was 0.06%, the wash water had a mixed calcium and magnesium hardness of a total of 200 ppm as calcium carbonate, and the water temperature was 24 ° C.

The laundry consisted of: 100% cotton; 100% polyester; 85% acetate and 15% nylon; and 65% polyester and 35% cotton.

The laundry was inspected in the wet state and after drying on a clothesline (drying on a clothesline often gives more visible residues than drying in an automatic dryer). No residue was observed in any of the cases. When the control detergent-. When tested, a moderate residue was observed on all specimens.

The results of the above-described practical experiment on 40 residues were verified by weighing the residue deposited on a sample of denim fabric. In this experiment, the detergent composition of the invention was filtered through a sample of denim material, the detergent being in solution suspension at a concentration of 0.12% in water with a hardness of 200 ppm (as CaCO 3) and at 24 ° C, and the weight of the residue on the fabric was noted and compared. In this experiment, the percentage residue, compared with the control experiment, was about 75%, which can be considered a significant difference in relation to washed banknotes.

The adhesion test, previously mentioned, in which the tackiness of the detergent product is measured, is a test in which 10 g of the base beads (or the detergent composition in some cases) are placed evenly between two watch glasses, both of which have a diameter of 23 cm, with a weight of of 500 g on top of the upper watch glass (the glasses with the concave side up). After standing for 5 minutes, the weight and the upper watch glass are removed, and the lower watch glass is turned upside down, after which the product that remains adhering to this watch glass is weighed. The percentage adhesion is the number of grams of the product left on the watch glass multiplied by 10.

Flow index is obtained by a flow test in which the volumetric flow rate of the base beads (and in some cases the final product) and of standardized Ottawa sand (-20 +60, US sight series) is compared by measuring the times required to completely empty a 1.9 liter Mason jar via a 2.2 cm diameter hole in a nozzle attached to the lid of the jar. Flow index in% is the time of sand flow divided by the time of flow of the test product times 100. 10 15 20 25 30 452 629 v .q - 41 Example 2 Base beads similar to those of Example 1, but containing NTA instead of part of the carbonate and the bicarbonate, was prepared using essentially the same method as described in said example. The composition was changed only by exchanging 5 parts of zeolite, 12 parts of sodium bicarbonate and 3 parts of sodium carbonate in the mixture for 20 parts of NTA in the form of the trisodium monohydrate salt.

, NTA was added after the sodium carbonate during the actual mixing process. The base beads obtained were not as fragile as those of Example 1, but they were satisfactory and sufficiently free-flowing. Instead of the final detergent composition containing 19.7% nonionic active detergent, in this case a content of 12% was sufficient, whereby the final percentages of the other components were increased accordingly. The resulting product was a satisfactory highly effective atomized detergent.

As a variation of this composition, 2.5% aqueous sodium silicate was subsequently added to the product, due to its corrosion protection properties and ability to bind magnesium ions in the wash water. Provided that the silicate has approximately the same particle size and density, it does not separate or segregate from the other bead detergent components during transport and storage, and the resulting product meets the specifications of a highly efficient commercial detergent, but a small quantity of zeolite-silica aggregate may be present. on washed materials.

In another alternative composition, 3% sodium silicate with a Na 2 O: SiO 2 ratio of about 1: 2.4 was included in the final product by adding an aqueous solution thereof to the mixer, together with 1.5% magnesium sulphate and 0.4% citric acid to prevent gelation or solidification in the mixer. The final product was a good high efficiency detergent, but it deposited more zeolite-silicate aggregates on washed materials dried on a clothesline than was the case with a comparable composition to which the aqueous sodium silicate was subsequently added.

Example 3 The procedure of Example 2 was repeated but pentasodium tripolyphosphate was substituted for NTA. The products obtained were good detergents with a bulk volume of about 0.8 g / cc (as well as the same according to Example 2), but the bulk volume could be varied by moderating the conditions of the spray tower and the composition so that it was in the range 0.7 0.9 g / cc and in some cases it could be as low as 0.3 g / cc. With the subsequently added silicate, the bulk volumes can be slightly higher, especially for the lower part of the area. The product was more free-flowing than that according to Example 2, but approximately equivalent to the same in terms of washing ability.

To the composition as above and the same as in previous examples, an additional quantity of bentonite can be added to the mixture in the mixer to obtain products containing 15% (or more) of bentonite. These products are even better in terms of the cohesive effect, dispersibility and other desirable properties that can be attributed to the bentonite and they are good detergent products (and base beads). The tripolyphosphate can also be replaced, either in whole or in part, e.g. l / 2, against tetrasodium pyrophosphate, whereby the same good products are obtained. 10 15 20 25 30 452 629 - u -Q. Example 4 A final detergent product was prepared, essentially as described in Examples 1 and 2, containing 30 parts of zeolite, 30 parts of NTA, 20 parts of nonionic detergent, 10 parts of bentonite, 5 parts of sodium carbonate, 5 parts of water and 1 part. 3 parts enzyme. This product had a bulk volume of about 0.5 g / cc and was a satisfactory detergent. However, in order to improve the flowability of the product, it was appropriate to reduce the content of nonionic detergent to 15% and preferably 12%. To increase the bulk volume to about 0.7, half the amount of bentonite could be exchanged for sodium silicate (Na 2 O: SiO 2 ratio 1: 2.4), which was added as the last component in the mixer in the form of a 47.5% aqueous solution. and 1.5 parts of magnesium sulphate and 0.4 parts of citric acid could similarly be added as anti-gelling agents earlier in the preparation of the mixture itself. The resulting product had a bulk volume of about 0.7 g / cc and could absorb about 20 parts of nonionic detergent without becoming tacky or having reduced flowability. Although it deposits less zeolite-silicate agglomerates than compositions with the conventionally higher levels of silicate added to the mixer, the agglomerate can be found on laundry washed with the product and dried on a clothesline.

Example 5 Instead of preparing base beads to which the detergent is applied to give a detergent composition, the composition can be spray dried directly from the mixer, including a suitable synthetic organic detergent in the mixture. Using essentially the same procedure as described in Example 1, a mixture was prepared which was spray dried to detergent beads containing 16 parts of linear tridecylbenzenesulfonate, 20 parts of zeolite, 12.5 parts of bentonite. 15 parts NTA, 10 parts sodium carbonate and conventional adjuvants (dye, fluorescent bleach). The bulk volume of this spray-dried product is in the range 0.3 - 0.8, normally in the lower part of this range and can sometimes be as low as 0.2 g / cc. In the manufacturing process, the organic detergent should generally be added after the water. The drying should usually take place to a moisture content of about 8 - 12%.

To the resulting product is preferably added about 3 parts by weight of aqueous sodium silicate, together with other normal adjuvants, such as enzymes and perfume. This is a satisfactory highly efficient detergent, which does not deposit excessively large amounts of zeolite or zeolite-silica aggregates on washed fabrics. Due to the presence of bentonite, the detergent appears to disperse very rapidly when added to the wash water, and it is believed that, at least in part, the rapid dispersion together with the presence of bentonite tends to inhibit the deposition of zeolite.

Example 6 The same procedure was used as in Example 5, but NTA was exchanged for the same amount of calcined soda. This product was also a satisfactory highly effective detergent.

Example 7 The same procedure was used as in Example 5, but pentasodium tripolyphosphate was used instead of NTA. The product produced was extremely free-flowing and constituted a good highly active synthetic organic detergent composition. If it is desired that silicate be included, this should be 15 20 25 30 452 629 u __. Is preferably added retrospectively in the form of an aqueous sodium silicate, but up to 5 parts of silicate may be added to the mixer together with suitable quantities of magnesium sulphate and citric acid, as described in previous examples, to obtain useful detergent compositions, although some deposition of zeolite silicate may occur.

In addition to the conventional materials which can be added afterwards, plasticizing quantities of a cationic material can be added to the product according to this example (and to the products according to other examples), e.g. 8% dimethyl distearylammonium chloride, an amphoteric detergent, e.g. 5% Miranol C2M (1-carboxymethyl-1-carboxyethoxyethyl-2-coconut-imidazolinium betaine), or a bleaching agent, e.g. 15% sodium perborate (preferably activated). The additions of these materials naturally reduce the levels of the other components in the final product, whereby the properties of the composition can be changed slightly so that sometimes a larger amount of the product must be used in the washing water to achieve the same cleaning effect.

In Examples 5 to 7, the linear tridecylbenzene sulfonate can be exchanged for the same amount by weight of sodium lauryl sulfate or sodium lauryl polyethoxy sulfate (3 to 10 EtO) or mixtures of these materials in equal parts, the resulting products also being useful as detergent compositions.

Also, instead of NTA, carbonate, carbonate and bicarbonate, as well as polyphosphate, sodium citrate and / or sodium gluconate can be replaced, at least in part, e.g. l / 4, l / 2, and good detergents are obtained.

Example 8 The products of Example 1 and Example 7 (the primary, first described products) were mixed in equal quantities to give a final product having the properties of the two ingredients. Prior to mixing, the materials to be blended had approximately the same bulk volume, approximately 0.5 g / cc, and approximately the same particle size, within the No. 10 - 60 range of the US screen series, to prevent separation during transport and storage. This mixed product is especially suitable when it comes to removing both oil-based and clay-based stains on laundry, it is free-flowing, stable and attractive. In some cases, one of the different starting materials may be colored or pigmented while the other may retain its natural color, in order to achieve special effects in terms of appearance. In addition to the particle size and the bulk volumes being approximately the same, the moisture contents should preferably also be approximately the same, e.g. about 10%, so that the migration of moisture between the different beads is small.

Among the materials used in Example 7, the anionic detergent consisting of sodium alkylbenzene sulfonate can be exchanged for a sodium alpha-olefin sulfonate (14-15 carbon atoms in the olefin) or for a sodium paraffin sulfonate (12-15 carbon atoms in the paraffin) and also this mixture are useful as detergents.

Example 9 Using essentially the same procedure as in Example 1, a mixture of 36.9 parts of water, 1.2 parts of fluorescent bleach (Tinopal SBM, extra concentrated) was prepared, 0.1 part of ultramarine blue, 2.1 parts of magnesium sulphate (heptahydrate), 0.3 parts of sodium citrate, 22.4 parts of zeolite 4A powder (partially hydrated, to about 20% moisture content), 20.9 parts of trisodium nitrile triacetate monohydrate, 10.4 parts of a 47 , 5% solution of sodium silicate solids (Na2O: SiO2 = 1: 2.4), 3.7 parts sodium bentonite (previously sold as THIXO-JEL No. 2), 2.8 parts natural calcined soda and 2.1 parts mineral compound, which can help increase the porosity of the beads, and as a detergent. The mixture was spray-dried in the same manner as described previously, the water loss during drying being about 45.2%.

On 78.4 parts of the spray-dried base beads, with the particle size in the range No. 10 - 100 (sieved), 20 parts of Neodol 23-6.5 were sprayed, after which the beads were mixed with 1.3 parts of highly active proteolytic enzyme, and 0.3 parts. detergent perfume was sprayed on them. The final product had a zeolite content of 25%, an NTA content of 30%, a sodium bentonite content of 5% and a water soluble sodium silicate content of 5%. The water content was 5% and the content of the active detergent component (polyethoxylated higher fatty alcohol) was 20%. The bulk volume was about 0.7 g / cc and the pH of a 1% solution was about 10.

A detergent composition prepared in this way is a satisfactory highly active nonionic detergent, but it gives slightly larger deposits of zeolite-silicate aggregates on washed fabric dried on a clothesline than is the case with a corresponding composition prepared without any water-soluble solid silicate. Preferably, such a corresponding composition should also contain about 0.1 - 0.5% of a low molecular weight sodium polyacrylate of the type previously described. Both products provide a good washing of the laundry and are particularly effective in cold washing water, at least in part due to the bentonite content therein and the almost instantaneous dispersion which can be ascertained when the detergent is added to the 452 629 M 48 wash water (which dispersion also reduces the time for any reaction between soluble silicate and zeolite and the formation of unwanted aggregates).

Claims (28)

452 629 v »49 P a t e n t k r a v Free-flowing spray-dried bead material, useful as a detergent composition or for the preparation of a finely divided detergent synthetic organic detergent composition by adding a synthetic organic detergent to the bead material, characterized in that it contains 5 to 60% by weight of water-softening zeolite; 40% by weight of bentonite which acts as a binder for the spray-dried beads and which contains sufficient water to facilitate the dispersion of the bentonite, 5 to 60% by weight of water-soluble detergent-active salt or a mixture thereof salts, 0 to 30% by weight of water-soluble organic detergent and 0 to 5% by weight of water-soluble silicate, the content of water-soluble silicate being low enough to prevent unacceptable deposition of zeolite-silicate reaction product on washed laundry. Bead material according to claim 1, characterized in that when no water-soluble synthetic detergent is present, the water-soluble detergent salt consists of polyphosphate, pyrophosphate, orthophosphate, borate, nitrile triacetate, gluconate or citrate or a mixture of two or more of these. Bead material according to claim 2, with a bulk volume in the range 0.2 - 0.9 g / cc and particle sizes in the range 10 - 100 according to the US screen series, characterized in that the water-softening zeolite is a hydrated water-softening zeolite containing 10 15 20 25 30 4s2_e29 .I 50 15 - 25% by weight of hydrate water and having a calcium ion exchange capacity in the range 200 - 400 mg eq calcium carbonate hardness per gram of anhydrous zeolite, the bentonite is a swelling clay with a swelling capacity in water of 3 - 15 ml / g and a viscosity of 3 - 30 cp at 6% concentration in water and includes at least 2% water based on anhydrous bentonite, a water-soluble detergent salt is present, which is a polyphosphate, pyrophosphate, orthophosphate, borate, nitrile triacetate, citrate, gluconate, carbonate or bicarbonate or a mixture of two or more of these, and the water-soluble silicate is an alkali metal or M-silicate with the M2O: SiO2 ratio in the range 1: 1, 6 to 1: 3. Bead material according to claim 3, characterized in that the ratio of bentonite to zeolite is in the range 1: 4 to 1: 1, the ratio of water-soluble detergent salt to zeolite is in the range 1: 2 to 3: 1, and the ratio between bentonite and water-soluble detergent salt is in the range 1:10 to.1¿1. Bead material according to claim 4, characterized in that it contains 10 - 40% by weight of hydrated sodium zeolite, 2 - 35% by weight of bentonite, the bentonite being of a type having a swelling capacity in the range 7 - 15 ml / 9 and a viscosity in the range 8 - 30 cp at a 6% concentration in water, 10 - 50% by weight of water-soluble detergent alkali metal salt or mixtures thereof, 0 - 25% by weight of water-soluble synthetic anionic organic detergent and 0 - 3 weight% water soluble silicate. Bead material according to claim 5, characterized in that it contains 15 ~ 35% by weight of zeolite A, 5 - 20% by weight of processed Wyoming bentonite, 20 - 50% by weight of water-soluble detergent sodium salt or mixtures thereof, 15 20 25 30 35 452 629 _. 5 to 20% by weight of water-soluble synthetic anionic organic detergent and 0% sodium silicate, the ratio of bentonite zeolite being in the range 1: 3 to 2: 3, the ratio of water-soluble detergent salt zeolite being in the range of 2: 3 to 2: 1 and the ratio of bentonite: water-soluble detergent salt is in the range of 1: 6 to 1: 2. know that the water-soluble detergent active salt is selected from The bead material according to claim 2, the group consisting of carbonate, bicarbonate, polyphosphate or nitrile triacetate or a mixture thereof, and the bentonite includes at least 3% by weight of water based on anhydrous bentonite. Bead material according to claim 7, characterized in that the bentonite includes at least 4% by weight of water, the water-soluble detergent salt consists of a nitrile triacetate and no water-soluble synthetic organic detergent or any water-soluble silicate is present. characterized in that it contains 15 - 40% by weight of hydrated zeolite A comprising 15 - 25% by weight of hydrated water and with a Bead material according to claim 8, exchange capacity with respect to calcium ions in the range 200 - 400 mg eq calcium carbonate hardness per gram of anhydrous zeolite, 10 - 20% by weight of bentonite which is a processed Wyoming bentonite with a swelling capacity in the range 7 - 15 ml / g and with a viscosity in the range 3 - 30 cp at 6% concentration in water, and 20 - 60 wt% NTA. Bead material according to claim 7, characterized in that the bentonite includes at least 4% by weight of water, the water-soluble detergent salt consists of polyphosphate, and no water-soluble synthetic organic detergent or water-soluble silicate is present. 11. ll. Bead material according to claim 10, characterized in that it contains 20 - 40% by weight of hydrated zeolite A 10 15 20 25 30 452 529 52 comprising 15 - 25% by weight of hydrated water and having a yield capacity with respect to calcium ions in the range 200 - 400 mg / eq calcium carbonate hardness per gram of anhydrous zeolite, 10 - 20% by weight of bentonite which is a processed Wyoming bentonite with a swelling capacity in the range 7 - 15 ml / g and a viscosity in the range 3 - 30 cP at 6% concentration. concentration in water, and 20-60% by weight of sodium tripolyphosphate. 12. A bead material according to claim 2, characterized in that it contains S - 30% by weight of water-soluble synthetic organic detergent. Pearl material according to claim 12, characterized in that the water-soluble synthetic organic detergent is an anionic detergent. 14. l4. Bead material according to claim 13, characterized in that the anionic detergent is linear sodium sodium benzenesulfonate in which the oxylalene has 10 to 18 x atoms, sodium fatty alcohol sulphate in which the alcohol moiety has 10 to 18 carbon atoms, or sodium fatty alcohol sulphate ethoxylate 10 to 18 carbon atoms and containing 3 to 30 ethylene oxide groups per mole, or a mixture of two or more of these, the content of the anionic detergent (s) in the beads being between 5% and 25% by weight. Pearl material according to claim 7, characterized in that it contains 3 to 30% by weight of water-soluble synthetic anionic organic detergent. The bead material according to claim 15, characterized in that the anionic detergent is linear alkylbenzene sulfonate in which the alkyl moiety has 10 to 18 carbon atoms, nat. 53 fatty alcohol sulphate in which the alcohol moiety has 10 to 18 carbon atoms, or sodium fatty alcohol ethoxylate sulphate in which the fatty alcohol moiety has 10 to 18 carbon atoms and which contains 3 to 30 ethylene oxide groups per mole, or a mixture of two or more thereof, the content of the anionic detergent ) the beads are between 5 and 25% by weight. Bead material according to claim 7, characterized in that it does not contain water-soluble synthetic organic detergent or water-soluble silicate. 18. Bead material according to claim 2, characterized in that it contains 0.05 - 1% by weight of polyacrylate with a molecular weight in the range 1000 - 5000. Bead material according to claim 3 with a bulk volume in the range 0.2 - 0.8 g / cc, characterized in that the zeolite is hydrated zeolite A, the bentonite comprising at least 3% by weight of water based on anhydrous bentonite, the water-soluble detergent salt is a sodium salt of nitrile triacetic acid, the water-soluble silicate, if present, is sodium silicate with the Na 2 O: SiO 2 ratio in the range 1: 2 to 1: 2.8, the water content of the beads is between 3 and 12% by weight thereof, the ratio of bentonite: zeolite is in the range of 1: 6 to 1: 2, the ratio of NTA: zeolite is in the range of 1: 2 to 2: 1, and the ratio of bentonite: NTA is in the range of 1: 6 to 1 : 2, the percentages of hydrated zeolite, bentonite, sodium nitrile triacetate and silicate being in the ranges 10 - 40% by weight, 2 - 25% by weight, 10 - 40% by weight and 0 - 5% by weight, respectively. Bead material according to claim 3 with a bulk volume in the range 0.2 - 0.8 g / cc, characterized in that it contains 5 - 30% by weight of synthetic anionic organic matter. detergent, and the zeolite consists of hydrated zeolite A, the bentonite includes at least 3% by weight of water based on anhydrous bentonite, the water-soluble detergent salt is a sodium salt of nitrile triacetic acid, the synthetic anionic organic detergent is linear sodium alkylbenzenesulfonate - in which the alkyl moiety has 18 carbon atoms, sodium fatty alcohol sulphate in which the alcohol moiety has 10 to 18 carbon atoms or sodium fatty alcohol ethoxylate sulphate in which the fatty alcohol moiety has 10 to 18 carbon atoms and which contains 3 to 30 ethylene oxide groups per mole, or a mixture of two or more thereof, the water-soluble silicate, if such sodium silicate with the Na 2 O: SiO 2 ratio is in the range 1: 2 to 1: 2.8 and the water content of the beads is between 3 and 12% by weight thereof, The bentonite: zeolite is in the range of 1: 6 to 1: 1, the ratio of NTA: the zeolite is in the range of 1: 3 to 3: 1, the ratio of bentonite: NTA is in the range of 1:10 to 1: 1 and the ratio of synthetic anionic organic deter gentzzeolite is in the range 1: 1 to 1: 4, and the percentages of hydrated zeolite, bentonite, sodium nitrile triacetate, synthetic anionic organic detergent and silicate are in the range 10 - 40% by weight, 2 - 25% by weight, 10 - 40% by weight, 10 - 25% by weight and 0 - 5% by weight, respectively. Bead material according to claim 3 with a bulk volume in the range 0.2 - 0.8 g / cc, characterized in that the zeolite is hydrated zeolite A, the bentonite includes at least 3% by weight of water based on anhydrous bentonite, the water-soluble detergent salt is pentasodium tri-polyphosphate or tetrasodium pyrophosphate or a mixture thereof, the water-soluble silicate, if such a 2O: SiO2 ratio in the range 1: 2 to 1: 2.8, and the water content is present, is sodium silicate with Na 20 25 30 452 629 _. The 55 beads are between 3 and 12% by weight thereof, the ratio of bentonite zeolite being in the range of 1: 6 to 1: 2, the ratio of total polyphosphate zeolite being in the range of 1: 2 to 2: 1 and the ratio of bentonite: total polyphosphate is in the range 1: 6 to 1: 2, and the percentages of hydrated zeolite, bentonite, total polyphosphate and silicate are in the ranges 15 - 35% by weight, 5 - 20% by weight, 15 - 40% by weight respectively 0 - 5% by weight. Bead material according to claim 3 with a bulk volume in the range 0.2 - 0.8 g / cc, in that it contains 5 - 30% by weight of synthetic anionic organic detergent, and the zeolite is hydrated zeolite A, the bentonite includes at least 3% by weight of water based on water-characterized free bentonite, the water-soluble detergent salt is pentasodium tripolyphosphate or tetrasodium pyrophosphate or a mixture thereof, the synthetic anionic organic detergent is linear sodium sodium alkylbenzene sulfonate in which hollow sulphate in which the alcohol moiety has 10 to 18 carbon atoms or sodium fatty alcohol ethoxylate sulphate in which the fatty alcohol moiety has 10 to 18 carbon atoms and which contains 3 to 30 ethylene oxide groups per mole, or a mixture of two or more thereof, and the water-soluble silicate, if present, the sodium silicate with the Na % of it, and the ratio of bentonite: zeolite is in the range of 1: 6 to 1: 1, the ratio of total polyphosphate zeolite is in the range of 1: 3 to 3: 1, the ratio of bentonite: total polyphosphate is in the range of 1:10 to 1 : 1 and the ratio of synthetic anionic organic detergent: zeolite is in the range 1: 1 to 1: 4, and the percentages of hydrated zeolite, bentonite, total polyphosphate, synthetic anionic organic detergent and silicate are in the range 10 - 40 10 15 4s2_e29 a1: 56% by weight, 2 - 25% by weight, 10 - 50% by weight, 10 - 25% by weight and 0 - 5% by weight, respectively. 23._Detergent composition, characterized in that it consists of a bead material according to claim 1 in which a nonionic detergent is absorbed, so that the percentage of the nonionic detergent in the composition is in the range 8 - 30% by weight. IN Detergent composition, characterized in that it consists of a bead material according to claim 2 in which a nonionic detergent is absorbed, so that the percentage of the nonionic detergent in the composition is in the range 8 - 30% by weight. Detergent composition according to claim 24, characterized in that the nonionic detergent is a condensation product of 6 to 12 moles of ethylene oxide and a higher fatty alcohol having 12 to 16 carbon atoms, the content of the nonionic detergent in the composition being within the range of council 10 -_25% by weight. Detergent composition, characterized in that it consists of a bead material according to claim 17 in which a nonionic detergent is absorbed, so that the percentage of the nonionic detergent in the composition is in the range 8 - 30% by weight. Detergent composition according to claim 26, characterized in that the nonionic detergent is a condensation product of 6 to 22 moles of ethylene oxide and a higher fatty alcohol having 12 to 16 carbon atoms, the content of the nonionic detergent in the composition being in the range of - 25% by weight. 452 629 '' _ _. .- 57 Detergent composition, characterized in that it consists of a mixture of the bead material according to claim 17 and a composition according to claim 26, with the particle sizes in the range No. 100-100 according to the US screen series and in a weight ratio in the range of 1: 10 to 10: 1- wherein the bulk volumes of the bead materials before mixing them are within 0.1 g / cc in relation to each other and to the bulk volume of the final composition, which is in the range 0.2 - 0.9 g / cc. k