SE444815B - A PHOSPHATE-FREE PREPARING, PARTICULAR, HIGH-EFFECTIVE DETERGENT AND PROCEDURE FOR ITS PREPARATION - Google Patents

Description

7810337-1 detergent compositions. In some situations they can partially replace phosphate builders and in other cases they allow a total replacement of such washers, sometimes in conjunction with other water soluble washers that do not provide nutritional supplements in lakes and other waterways which would lead to their overgrowth.

The detergent composition of the present invention is characterized in that the detergent composition has a bulk density of more than 0.6 g / ml and comprises a water-soluble nonionic detergent absorbed on spray-dried grains consisting of a mixture of said zeolite and either sodium carbonate or a mixture of sodium carbonate and sodium bicarbonate. in a weight ratio in the range 3: 8 - 5: 1, said spray-dried grains containing between 2 and 15% by weight of water and so that the weight proportions between zeolite and sodium carbonate are between 1: 0, 1 and 1: 1, 5, or so that the weight proportions of zeolite and sodium carbonate together with sodium bicarbonate are between 1: 0.5 and 1: 3.6, and in which the grain proportions of zeolite, sodium carbonate and sodium bicarbonate are between 1: 0.3 and 1.6: 0, 2 - 2.0 calculated on anhydrous basis; wherein in the case of the spray-dried granules containing zeolite and sodium carbonate, these are mixed with 0.1 to 5 parts by weight of particulate hydrated sodium silicate, calculated on the anhydrous basis, with a Na2O: SiO2 molar ratio in the range 1: 1.5 to 1: 2 Before absorbing 0.2 to 1.6 parts of said nonionic detergent on the zeolite carbonate bicarbonate grains or before absorbing 0.2 to 1.5 parts of said nonionic detergent on the zeolite carbonate silicate grains.

In the present invention, a nonionic detergent is the primary surfactant and detersive material used, and an ion exchange zeolite is used as a detergent builder for such a detergent. In addition, suitable water-soluble builder salts are also present to further improve the properties of the detergent compositions prepared.

According to various preferred embodiments of the invention, builder salts include alkali metal pyrophosphate which comprises such ions which are unexpectedly effective in some proportions and in other builder salts in such compositions as a mixture case is the water-soluble builder alkali metal builder. and alkali metal bicarbonate or a mixture of alkali metal carbonates in certain proportions. In these latter cases, an excellent product is obtained without the need for phosphorus to be included in the composition.

The detergent composition of an ion exchange zeolite, reinforcing agent, a mixture of and alkali metal silicate according to the present invention comprises a nonionic detergent and an aqueous solution comprising alkali metal pyrophosphate or alkali metal carbonate and the alkali metal bicarbonate within the composition. of a portion of said zeolite to 0.1 - 2.5 parts of nonionic detergent to 0.2 - 5 parts of said water-soluble builder salt or salts, the proportions being such that the composition is free-flowing and effective as a detergent when used in hard water.

In the first of three preferred types of compositions of the present invention, the nonionic synthetic organic detergent constitutes about 8-25% of the composition, the ion exchange zeolite being a finely divided synthetic zeolite detergent builder of the formula (N 2 O 2) x '(Å 12 O 3) y' (SiO2) 2 ° wU2O where x is 1, y is from 0.8 to 1.2, 2 is from 1.5 to 3.5 and w is from 0 to 9, and constitutes 10 - 50% of the composition, wherein the water-soluble detergent salt is an alkali metal pyrophosphate, which constitutes about 10 - 50% of the composition. The ranges of the ratios of some zeolite to nonionic detergent and water-soluble builder salt are 0.16 - 2.5 and 0.2 - 5, respectively. In order to promote the free-flowing and fast-dispersing properties in such compositions, the alkali metal silicate content, if such silicate is used, is sufficiently low for not to affect such desirable properties. The nonionic detergent is preferably a higher fat alcohol polyoxyethylene ethanol, the higher fat alcohol having 12 to 18 carbon atoms and the polyoxyethylene group, including the endethanol thereon, having 5 to 15 moles of ethylene oxide per mole, and the zeolite may have a molecular formula as follows (Na 2 O) (Al2O3) 6- (SiO2) 12-27H2O while the alkali metal pyrophosphate salt is tetrasodium pyrophosphate and the silicate, when included, has a Na2O: SiO2 ratio in the range 1: 2 - 1: 3, the percentages of these constituents being 10 - 20, 10 - 30, 10 - 30 and 2 - 3%, respectively, and where 5 - 20% sodium carbonate, 10 - 40% sodium sulphate and 3 - 12% free moisture are also included. The product is preferably prepared in spray-dried granular form, but powders and granulated detergents are also useful. It is also preferred that the only organic detergent included be the nonionic detergent or a mixture of nonionic detergents, and that the only phosphate builder salt be tetrasodium pyrophosphate. Although the presence of up to about 3.5% sodium silicate may be desirable for the purpose of corrosion inhibiting effect, it is intended that the present products contain no silicate at all.

Nonionic detergents are listed extensively in McCutcheon's Detergents and Emulsifiers, 1973 Annual and in Surface Active Agents, Vol. II, by Schwartz, Perry and Berch (Interscience Publishers, 1958). Such detergents are usually pasty or waxy solids at room temperature (20 ° C), which are either sufficiently water soluble to dissolve directly in water or will melt rapidly at the temperature maintained on the wash water, such as when this temperature is above 40 ° C.

The nonionic detergents used are usually not those which are normally liquid at room temperature, as such detergents would tend to give rise to a sticky product which would have poor dispersibility and clump or solidify during storage, but nevertheless small quantities of liquid detergents were sometimes used in a desirable manner. Typical useful nonionic detergents are the poly-Ggf (Alkenoxy) derivatives which are usually prepared by the condensation of lower (2-4 carbon atoms) -alkyl oxide, e.g. ethylene oxide, propylene oxide (with sufficient ethylene oxide to provide a water-soluble product) with a compound having a hydrophobic hydrocarbon chain and containing one or more active hydrogen atoms, such as higher-alkylphenols, higher-fatty acids, higher-fat mercaptans, higher-fatty amines and higher-fat polyols and alcohols, e.g. fatty alcohols having 8 to 20 or 10 or 12 to 18 carbon atoms in an alkyl chain and the alkoxylation is of an average of about 3 to 30, preferably 6 to 20 and more preferably 5 to 15 lower alkylene oxide units, e.g. ethylene oxide. Preferred nonionic detergents are those represented by the formula RO (C 2 H 4 O) n H 7810337-1. Wherein R is the residue of a linear saturated primary alcohol (an alkyl) having 12 to 18 carbon atoms and n is an integer from 6 to 20 or 5 to l5. The preferred nonionic detergents can be attributed to higher fatty alcohol polyoxyethylene ethanols (the terminal ethanol of these ethers is included in the number of oxyethylene groups counted in moles of the nonionic detergent). Typical commercial nonionic surfactants suitable for use in the compositions of the invention include Neodol 45-1, which is an ethoxylation product (having an average of about 11l of ethylene oxide units) with a fatty alcohol having an average chain. 14 - 15 carbon atoms (manufactured by Shell Chemical Company); Neodol 25-7, which is a fatty alcohol having a chain containing 12 to 15 carbon atoms and ethoxylated with an average of 7 ethylene oxide units; and Alfonid®) 18-18-65, which is an alkanol having 16 to 18 carbon atoms and ethoxylated with an average of 10 to 11 ethylene oxide units (Continental Oil Company). Also useful are the products called Igepal obtained from GAF Co., Inc. In the above description, higher, as used for higher alkyl, higher fat, etc., means that there are 8-20, preferably 12 - 18 carbon atoms.

The zeolites used in the present invention include the crystalline, amorphous and mixed crystalline-amorphous zeolites of natural or synthetic origin or mixtures thereof which may have satisfactorily rapid and sufficiently effective action to counteract hardening ions. Such materials are preferably capable of reacting rapidly enough with a hardening cation, such as any of the calcium, magnesium, iron ions or the like, to soften the wash water before adverse reactions occur between such hardening ions and any of the constituents of the synthetic organic detergent compositions. prepared according to the present invention.

A useful range for calcium ion exchange capacities is from about 200 mg equivalents of calcium carbonate hardness per gram of aluminosilicate to 400 or more such milligram equivalents (calculated on an anhydrous basis). A preferred such range is about 250-350 milligram-equivalent per gram. The water-insoluble crystalline aluminum silicates used are often characterized in that they have a network of pores of substantially uniform size in the range of about 3 to 10 Å angstroms, often about 4 Å (nominal), this size being determined by the unit structure. in the special type of zeolite containing 2 or more such a peculiar manner of zeolite crystal. networks with different pore sizes can of course also be used satisfactorily, as well as mixtures of such crystalline materials with each other and with amorphous materials. the Zeolite should be a monovalent cation exchange zeolite, i.e. should be an aluminosilicate of a monovalent cation such as sodium, potassium, lithium (whenever possible) or before alkali metal, ammonium or hydrogen. The monovalent cation of the zeolite molecular sieve is preferably an alkali metal cation, especially sodium or potassium, and most preferably it is sodium, but a variety of other types are also useful.

Crystalline types of zeolites useful as molecular sieves in the invention include, at least in part, zeolites of the following crystal structure groups: A, X, Y, L, mordenite and erionite, of which types A and X are preferred. Mixtures of such molecular sieve zeolites may also be useful, especially when type A zeolite is included. 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 in 1974 by John Wiley & Sons. Typical commercially available zeolites of the aforementioned structural 749 in n fl la q fl nrxqpräums in Table 9 item 6 on pages 747 - said book.

The zeolite used in the invention is preferably synthetic and it is also preferred that it be of type A or similar structure, as specifically described on page 133 of said book. Good results have been obtained when a molecular sieve zeolite of type 4A has been used, where the monovalent cation of the zeolite is sodium and the pore size of the zeolite is about 4 Angstroms. Molecular silzeolites can be prepared in either a dehydrated or calcined form containing from about 0 or about 1.5% to about 3% moisture or in a hydrated or aqueous form containing additional bound water in an amount of from about 4 up 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 is preferred in the practice of the present invention. The preparation of such hydrated crystals is well known in the art.

In the preparation of Zeolite A, as indicated above, for example, the hydrated zeolite crystals formed in the crystallization medium (such as an aqueous amorphous sodium aluminum silicate gel) were used without the high temperature dehydration (calcination to 3% or less water content) normally performed. in the case of crystals / such crystals for use as catalysts, e.g. cracking catalysts. The crystalline zeolite, in either fully hydrated or partially hydrated form, can be recovered by filtering out the crystals from the crystallization medium and Unkackmii air at ambient temperature or other suitable temperature so that their water content becomes the desired one, which water content is usually in the range of about 5 to 30% moisture, preferably 15 to 22%.

However, since at least partial hydration can sometimes occur during the preparation of the compositions of the present invention, the moisture content of the molecular sieve zeolite used may sometimes be as low as 0% at the beginning of the manufacturing process of the present detergent compositions and sometimes anhydrous zeolite may be included in the final product.

The zeolite to be used is preferably present from the beginning in a finely divided state, the final particle diameters being below 15 microns, e.g. 0.001 - 15 microns, preferably 0.01 - 10 microns and especially preferably 0.01 - 8 microns in average particle size, e.g. 4 - 8 microns, if it is crystalline and in 0.01 - 0.1 microns, e.g. 0.01 - 0.05 microns if it is amorphous. Although the crystalline synthetic zeolites are more common and better known, amorphous zeolites can be used instead and are often superior to crystalline materials with respect to a variety of important properties, as will be described, as well as the mixed crystalline-amorphous materials and mixtures of the different types of zeolites described. The particle sizes and pore sizes of such materials are usually the same as those described previously, but variations from the ranges described may be made, provided that the materials function satisfactorily as washers in the present compositions and do not remarkably make colored materials for whites. these materials are treated in aqueous medium. Although the formula for some amorphous zeolites may be represented as follows M 2 O-Al 2 O 3 - (SiO 2) 2 -WH 2 O wherein M is a monovalent cation, preferably an alkali metal, z is from 1.5 or 2.0 to 3.8 or 4 (2 is sometimes preferred) and w is from 2.5 to 6, especially when M is sodium, this formula can be changed as follows (Na 2 O) x- (Al 2 O 3) y- (SiO 2) Z-wH 2 O and usually, when x is 1, is y from 0.8 to 1.2, 2 from 1.5 to 5 and w is 0 to 9, these limits being preferably 0.9 to 1.1, 2.0 to 3.8 and 2.5 to 6. or 3.0 to 4.5 when x is 1. The chemical formula or structural formula is preferably the following or approximately the following formula: but the moles of water present may be 20 to 27, e.g. 24 to 27. Note that in this chemical formula the ratio x: y: 2: w is equal to 1: 1: 2: 4.5. 7810337-1 “10 The pyrophosphate builder salt is a salt of pyrophosphoric acid, H4P2O7.

Preferably the alkali metal salts are used and of these, the sodium salts are the more preferred, with those in which the acidic hydrogen atoms are completely neutralized being the most preferred. Although Na2H2P2O7 and Na3HP2O7 and the corresponding potassium salts can be used or may be included in certain pH values, it is pyrophosphate that is normally and most preferably used Na4P2O7. The anhydrous form of the salt or a hydrated form thereof, such as Na 4 P 2 O 7 - 10 OH 2 O, may be used as well as mixtures thereof or salts at intermediate stages of hydration.

The silicate may be any suitable water-soluble silicate and is preferably an alkali metal silicate, more preferably a sodium silicate, the ratio of alkali metal oxide to silica in the silicate being in the range 1: 1, 6 - 1: 3.8 or - 1: 4 and is preferably 1: 2 - 1: 3, more preferably about 1: 2.4, e.g. l: 2.35. Thus, a most preferred silicate is that having a Na 2 O: SiO 2 ratio of about 1: 2.4.

Although the essential components of the present heavy duty builder saline detergent compositions are the nonionic detergent, zeolite and pyrophosphate, with a small proportion of silicate also constituting a desirable component, almost always contain some free moisture which may or may not include dehydration water. different components of the compositions. Such moisture can be removed by heating to a temperature of 105 ° C for 5 minutes. In addition to moisture, other preferred additional components of the present compositions include alkali metal carbonate, alkali metal sulfate and other common auxiliary additives commonly used in the preparation of synthetic detergent compositions. The carbonate is usually sodium carbonate and this is usually included as calcined soda, but is hydratable to the monohydrate and decahydrate.

Instead of the carbonate, the sesquicarbonate can often be used, but the amount thereof used is usually greater than that of the carbonate, e.g. 1.2 - 3 times as much. Mixtures of carbonate and sesquicarbonate, sometimes with additional bicarbonate, may be used and alkali metal salts other than the sodium salts of these compounds may be used, but the sodium salts are highly preferred. Similarly, with respect to alkali metal sulfates, the sodium and potassium salts and mixtures thereof may be utilized, but the sodium salts are highly preferred. These can be used as sintered salt, in the anhydrous form or as the sodium sulphate decahydrate, or in some cases, as the bisulphate, in anhydrous form or as the monohydrate. When the bisulphate is used, the amount of this is normally about the same as that of the sulphate it is to replace.

A variety of excipients that can be used with other ingredients in the present compositions include the conventional functional and aesthetic excipients, such as bleaching agents, e.g. sodium perborate; dyes, e.g. pigments, dyes and optical brighteners; foam stabilizers, e.g. alkanolamides such as lauric acid myristic acid diethanolamide; enzymes, e.g. proteases; skin protective and skin conditioning agents, such as water-soluble low molecular weight proteins obtained by hydrolysis of proteinaceous materials such as animal hair, animal skins, gelatin, collagen; defoamers, e.g. silicone; textile plasticizers, e.g. ethoxylated lanolin; bactericides, e.g. tetrabromosalicylanilide; opacifiers, e.g. pelysterensuzpexxiesef, Lehensyra; buffering agents, e.g., alkali metal borates; perfumery; and dispersibility improvers, e.g. malda leror.

The proportions used by the various components of the present compositions are usually about 8-25% nonionic synthetic organic detergent, 10-50% zeolite and 10-50% pyrophosphate. The proportion of silicate, if included, is low enough to result in a product that is free-flowing, fast-dispersing and effective when used in hard water. These percentages are normally less than 3.5% silicate, preferably less than 3% and more preferably from about 2 to 39. Preferred ranges for the nonionic detergent, zeolite and tetrasodium pyrophosphate are 10-20%, 10-30%. respectively 10 - 30%, and when sodium carbonate (anhydrous), sodium sulphate and free moisture are included, the proportions of these are usually about 5 - 20%, 7810357-1 Q about 10 - 50% and about 3 - 15%, respectively, the more preferred the draw is 5 - 20%, 10 - 40% and 3 - 12% respectively. Thus, a preferred formulation may contain about 15% of the nonionic detergent, about 20% zeolite builder, about 25% tetrasodium pyrophosphate, about 3% sodium silicate, about 10% sodium carbonate, about 15% sodium sulfate and about 10% moisture.

When auxiliary additives are included, they are normally limited to a total proportion of about 10% of the product, preferably 5% thereof, and the individual auxiliary additives are usually less than 5%, preferably less than 2% and often most preferably less than 1% of the product. . All weights left are on the anhydrous component - "like" the product base.

The invented detergent compositions can be prepared and prepared according to a variety of suitable methods. Thus, according to one embodiment of the invention, the various components may be mixed together only as by mixing the pyrophosphate and zeolite, together with the carbonate and sulphate, if these are included, plus any powdered auxiliary additives. mixer sprays an aqueous solution of silicate (powdered silicates can also be used and can only be mixed in together with the other powder materials) and / or an aqueous solution of the nonionic detergent or a melt thereof, the temperature of this solution normally being in the range of 70 DEG C., preferably 40 DEG-60 DEG C. A variety of other mixing techniques of a similar nature may be employed.

The zeolite can be baked together by tumbling in a cylinder together with a binder or baking agent or liquid. In such approaches, the atomized zeolite, which has a particle size usually finer than 0.074 mm, agglomerates to particle sizes larger than 0.095 mm (160 mesh), e.g. 0.105 - 3.36 mm, preferably 0.149 - 1.68 mm. Instead of mixing or baking back the components of the detergent composition, it is often preferred that the composition be spray dried as far as possible, with only the nonionic detergent and other liquid constituents such as perfume being subsequently sprayed on a tumbling bed of the defuncted particles. The spray drying technique used is well known in the art and will be described in more detail below, when reference is made to the manufacturing techniques used to make the other types of products of the present invention.

The product of this embodiment of the present invention is unexpectedly superior to a variety of zeolite-containing and zeolite-free detergent compositions based on anionic detergent and pentasodium tripolyphosphate as a builder salt. Particularly when washing synthetic fabrics, such as nylon and polyester cotton fabrics with permanent pressure and when removing clay from such fabrics and cotton, the superiority of the invented compositions is obvious in comparison with similar compositions in which pentasodium tripolyphosphate is included instead of tetrasodium pyrophosphate. Thus, especially in the washing of synthetic textiles, such as nylon materials, polyester materials and blends of polyester and cotton, the use of the invented compositions enables a significant reduction of the phosphorus content in the detergent preparation and thereby helps the detergent manufacturers comply with laws and regulations limiting phosphorus use. . The silicate content of the present compositions is kept low enough to avoid poor dispersibility properties in the granular or granular product, while still being used as an anti-corrosion agent. It is particularly important that the silicate content is low, as the presence of the nonionic detergent, which can tend to make the product less free-flowing. However, since the present composition is less corrosive than a variety of other high performance detergent compositions, the smaller proportion of silicate normally used is still satisfactory in inhibiting corrosion of aluminum and other metal parts that may come into contact with the wash water. GGHOW the reduced proportion of silicate included, the product can dissolve more easily and faster without the effect of a silicate coating on the grains and without harmful reactions between the silicate and hardness-forming ions in the water, the zeolite, in which the water the fabrics are washed, and some other materials that includes. Although pyrophosphate would normally be expected to cause precipitation of certain product by reaction with calcium and / or magnesium hardening ions in the water, surprisingly pyrophosphate does not cause harmful deposits or precipitates on the materials being washed and does not cause the appearance in these materials becomes dull.

The surprising results obtained are considered to be due to the use of the nonionic detergent together with pyrophosphate and zeolite, and consequently it is preferred to use only nonionic detergent or a mixture of such detergents as the active detersive component and only pyrophosphate as a builder salt, although for some Applications The use of any tripolyphosphate may be desirable. The silicate, carbonate and sulphate may be omitted, but these components are usually included, the silicate for its anti-corrosion and slightly reinforcing properties, the carbonate for its hardness neutralizing and alkalizing properties and the sulphate for its filling and firming effects.

According to the second embodiment of the present invention there is provided a free-flowing phosphate-free particulate high performance detergent composition having a bulk density greater than 0.6 g / ml and comprising grains of ion exchange zeolite, sodium carbonate and sodium bicarbonate, in which grains the proportions of said composition - nents are in the range 1: 0, 3-1.6: 0.2-2.0, calculated on an anhydrous basis, whereby in the granules about 0.2 - 1.6 parts of nonionic detergent are absorbed. Such a product has been found to precipitate less residue on washed materials than is the case with a number of other high-performance detergent compositions in which comparable quantities of zeolite scrubbers are included. The present compositions can also be prepared in a characteristic spray-dried particulate form, which can contribute to their effectiveness as detergents and also their marketability. It is known that a useful detergent composition can be prepared by tumbling a mixed carbonate-bicarbonate salt, such as wegscheider's salt, together with nonionic detergent and coating the product with zeolite in powder form. However, such products may have a slightly different appearance compared to conventional detergents and would therefore not be so easily acceptable in the store. Spray-dried products also tend to be more uniform in composition and are manufactured with equipment that is generally available in facilities for the manufacture of detergents and which the operators are used to operating.

One method of preparing the present compositions comprises spray drying an aqueous mixture of ion exchange zeolite, sodium carbonate, sodium bicarbonate and water to a moisture content in the range of about 2 to 12% so that the proportions of zeolite, sodium carbonate and sodium bicarbonate in the spray dried grains produced are in the range 1: 0.3-1.6: 0.2-2.0, after which the granules are mixed with 0.2-1.6 parts of nonionic detergent in liquid form per part of zeolite so that this detergent is absorbed into in the grains.

The nonionic detergents used to provide the zeolite, carbonate, bicarbonate and nonionic detergent products of the present invention are substantially the same as those described; md aVSGOHÖG on the first-mentioned embodiment of the invention. Normally, however, liquid nonionic detergent can be utilized and a preferred nonionic detergent is Neodof® 25-6.5, which comprises 6.5 moles of ethylene oxide per mole of detergent. When the liquid nonionic detergents are applied to the base grains, they are preferably applied to grains which are hot enough for the liquid to penetrate into the interior of the grains, resulting in a product which has good spreadability properties. Preferred nonionic detergents of this embodiment of the invention are those having 5 to 20 and more preferably 5 to 12 lower alkylene oxide units per mole. The zeolites used are those previously described with respect to the first embodiment of the present invention.

The alkali metal carbonate and the alkali metal bicarbonate may be in the form of a mixture thereof, wherein both types of compounds are contained in the same individual grains or particles or may be separate.

Such materials suitably have particle sizes in the range of 0.149 - 0.84 mm, but a variety of other particle sizes, up to about 2.38 mm and as fine as 0.074 mm, may be used provided they dissolve and / or disperses rapidly and easily in the aqueous detergent mixture. Solutions can also be used provided that the moisture content of the detergent mixture prepared is thereby not made too high. Normally, the alkali metal (sodium or potassium) carbonates and bicarbonates, most preferred as sodium salts, are substantially anhydrous in preferred embodiments of the invention, but partially hydrated detergent salts of this type may also be used. The ratio of alkali metal carbonate to alkali metal bicarbonate, by weight, is generally in the range 3: 8 - 5: 1, preferably in the range 1: 2 - 2: 1, more preferably about 4: 3 in the finished product and of such proportions, plus about 40 to 60% e.g. about 50%, to 6 for the bicarbonate and minus 25 to 45%, e.g. about 35%, to 2 for the amounts of carbonate in the detergent mixture, so that the ratio therein becomes 3: 1 for bicarbonate: carbonate. The mixed salt, if used, can be made by a method which results in a substantial content, e.g. 10 - 100%, of Wegscheider's salt, any residue consisting of sodium bicarbonate. Such a product and the carbonate and bicarbonate components can be readily prepared into a suitable aqueous slurry together with the zeolite and water, which slurry is easily spray dried on particles which readily sorb nonionic detergent. Methods for preparing mixed carbonate-bicarbonate products, such as those obtained from Allied Chemical Corporation under the tradename Snowlite e.g. Snowlite I and Snowlite II, have been described in the patent literature.

The water in the detergent mixture and in the finished product is preferably deionized water or water which may be included as the solvent in aqueous solution or dispersion of one or more of the components of the detergent mixture. The water used, if any, is to be added; usually has a degree of hardness of less than 150 ppm, preferably less than 50 ppm and more preferably less than 10 ppm, calculated as calcium carbonate. Although deionized barrel water is preferred, tap water having a low hardness can also be used. The moisture content of the products is that which can be removed by heating to a temperature of 105 ° C for five minutes.

The alkali metal silicate which may be included in the compositions of the present invention is preferably sodium silicate having a Na 2 O: SiO 2 ratio in the range 1: 1, 6-3.2, preferably 1: 2 - 1: 3 and most preferably about 1: 2.4, e.g. l: 2.35.

Such a silicate can be added to the aqueous detergent mixture as an aqueous solution, usually containing about 40% sodium silicate as a solid. Alternatively, an equivalent of silicate may be added to the product afterwards, but this may result in somewhat less desirable properties of the finished product, such as increased residues on the washed materials in some cases, although this may also occur if the spray dried product is dried to an excessive extent and the silicate is dehydrated to an excessive extent.

In addition to the main ingredients of the compositions of this embodiment of the invention, which have already been described herein, a variety of supplemental builder salts, fillers and co-additives may be used, such as those previously described.

Among the preferred auxiliary additives are enzymes such as proteolytic and amylotic enzymes, fluorescent whitening agents and antifoulants. Examples of such materials are protease and amylase; sodium salts of diaminostilbene disulfonic acid and naphthotriazolyl stilbenes; and sodium carboxymethylcellulose (CMC).

The proportions of active ingredients in the final product should be in the range 1: 0.3-1.6: 0.2-2.0: 0.2-1.6 for zeolite: carbonate: bicarbonate: nonionic detergent. Normally the ratio of bicarbonate to carbonate is in the range 1: 2 - 2: 1. The percentages of the various constituents, including water, are 15 - 40% zeolite, 10 - 25% carbonate, 8 - 22% bicarbonate, 15 - 25% nonionic detergent and 2 - 10% moisture.

These ranges are preferably 20 - 30%, 15 - 25%, 10 - 20%, 18 - 22% and 4 - 8% respectively. The silicate content can be 3 - 20%, preferably 5 - 15%. The content of fluorescent bleach is normally in the range 0.05 - 3%, preferably 1 - 2.5% and the content of proteolytic enzyme (including the normal carrier for such an enzyme) is from 0.5 - 3%, preferably 1 - 2%. %, when such an enzyme is included. A variety of other adjuvants may also be included, but the total amount thereof should not normally exceed 5% and is preferably less than 3%, with the percentages of individual components being less than 1%, preferably 0.5% or less. Thus, 0.1 - 0.4% pigment can be included as well as 0.1 - 0.4% perfume. If appropriate, the percentage of the anti-redeposition agent may be as high as 3%, but normally the percentage of this ingredient, if included, is 0.5-2%.

The high bulk density particulate detergent product of the present invention is usually in the form of free-flowing round grains such as that obtained for other spray-dried products, although the interior of the grains may be substantially hollow. The particle sizes of the grains are normally in the range 0.095 - 3.36 mm (160 - 6 mesh according to US Standard), preferably 0.149 - 2.38, with less than 10%, preferably less than 5% and more preferably less than 1% of the product. outside these ranges. The bulk density of the finished detergent is normally at least 0.6 g / ml, preferably at least 0.065 g / ml and most preferably it is in the range 0.65 - 0.85 g / ml, e.g. 0.71 - 0.83 g / ml. The free-flowing ability of such products is excellent and it is usually better than 70% of the free-flowing ability of sand with similar particle size, normally 70-90% thereof and preferably 75-90% thereof. Although a bulk density in the range 0.65 - 0.85 g / ml is preferred, it can be changed up and down, e.g. to 0.5 - 0.9 g / ml, by changing the recipe and the techniques of spray drying.

In the preparation of the invented detergent, it is important that a sorbent grain be provided for the absorption of nonionic detergent therein. This sorption must be sufficient for the nonionic detergent to be introduced into the interior of the grain and therefore not tend to cause the grains to bake together or cause poor free-flowing properties. Although sodium carbonate of certain types has been found to be an excellent sorbent for nonionic detergents, products prepared with this sodium carbonate alone as a builder salt tend to have remarkably high pH values, at least when this sodium carbonate is used in the quantities needed to make compositions of the type that are acceptably detersive. The presence of bicarbonate together with the carbonate appears to be desirable in the preparation of a free-flowing and absorbent product as well as to solubilize the product, and in addition the bicarbonate exerts its buffering effect.

Some of the desirable properties of the product can be increased by a decomposition of a part of the bicarbonate during the production of the zeolite-carbonate-bicarbonate grains with the resulting separation of carbon dioxide from the product and / or the neutralization of any excess or locally occurring alkalinity by the released carbonic acid. . in the case of the spray-dried zeolite-sodium carbonate-sodium bicarbonate granules prepared according to the invention, the proportions of said constituents are in the range 1: 0.3-1.6: 0.2-2.0 as previously described for the finished product, the proportion between bicarbonate and carbonate is also the one previously provided. The bulk density of the spray dried beads or granules is normally 0.5 - 0.7 g / ml (without absorbing nonionic detergent). The moisture content of the grains is usually 2 - 15%, preferably 5 - 10%. The intervals for the contents of the other components similarly have limits which are higher than those specified for the finished product, the increase being a function of the proportion between the weight of the finished product and the weight of the spray-dried grains. In other words, if, for example, the finished product is identical in composition to the spray-dried product except for the incorporation therein (on the basis of a finished product) of 20% nonionic detergent, which is subsequently sprayed on the spray-dried granules and absorbed therein , the percentages of zeolite in the spray-dried grains must be 3l, 3% to give a product containing 25% thereof. It should be noted that the spray-dried base grains preferably do not contain any detersive component, such as synthetic organic detergent (including soap), and do not contain any surfactants such as wetting agents and emulsifying agents, as it has been found that such components to produce lower bulk density and in its interior less absorbent spray dried grains or beads.

The particle sizes of the produced grains are essentially the same as those of the grains in the finished product and their free-flowing capacity is at least 70% of that of sand with comparable particle size.

In the preparation of the absorbent spray dried detergent granules which nevertheless have a comparatively high bulk density, the spray drying operation is carried out in a normal manner, but when silicate is included and is to be spray dried together with the other base particle components a special procedure must be followed to incorporate the desired recipe. of silicate, in particular if this quantity is to be in the range of 8 to 20% and even more explicitly if it is to be in the range of 10 to 20%.

Ordinary mixing or so-called "crutching" of the base grain components, the zeolite, the carbonate and the bicarbonate, with or without small quantities of other non-surfactant components, such as stabilizers, bleaches and pigments, can be carried out in practice followed by conventional spray drying, whereby powdery silicate, such as aqueous silicate, e.g. aqueous sodium silicate, is added afterwards, usually together with other co-additives, such as enzyme powders, perfumes, anti-precipitating agents, e.g. sodium carboxymethylcellulose. In such processes with subsequent addition of components, it is normally desirable for the silicate to be mixed with the base grains before spraying on said grains the liquid-transferred or condensed nonionic detergent, perfume and other liquid components. However, it is generally better that the enzyme powder, anti-precipitating agent and other such components (which may be of smaller particle sizes than the base particles and may also be less absorbent than the base particles and the silicate powder) be applied after spraying the nonionic detergent onto the base particles. Nonionic detergent film on the surfaces of the base particles or in exposed underlying surface portions of these particles can help hold the powdered components on these particles, thereby preventing undesired separation and separation of components in the package.

Although silicate can be added to the base particles, usually in a mixer, such as a sloping cylinder or a Patterson-Kelley type mixer or double jacketed mixer, an improved product of the present composition, which forms little or no residue on clothes washed with the product, even when cold water is used, is prepared by incorporating the silicate into the detergent mixer and spray-drying it from an aqueous so-called "crutcher" mixture together with the rest of the base grain components. By following the procedure of the present invention, it is found that, despite the presence of significant quantities of silicate in the crutcher mixture, together with other detergent compositions, it has often formed a product with unsatisfactory dispersibility properties, which product may tend to to bake together, the present products are free-flowing and absorbent and are capable of forming free-flowing detergent compositions with high bulk density.

Whether or not the silicate is included in the "crutcher" mixture, such a mixture normally comprises 40-75% of solids and 25-60% of water. The detergent or crutcher mixer should generally be provided with a heat exchanger means so that the temperature of the mixture can be controlled. Normally the temperature is in the range from room temperature to 90 ° C, preferably 20-70 ° C and most preferably 45-65 ° C. The residence time in the crutcher mixer is usually in the range of 5 minutes to one hour, preferably 10 minutes to 30 minutes. When the silicate is included in the "crutcher" mixture, the carbonate, bicarbonate and water plus any other non-surfactant components to be included in the spray-dried base grains are mixed together, eg fluorescent whitening agents, pigments, which mixture usually takes place for a period of one minute to 10 minutes, preferably 3 to 7 minutes, and then the silicate is added slowly, preferably as an aqueous solution of 20-45%, more preferably 35-41% solids, eg 40%, wherein the addition takes place under 3 to 7 mouths, until a viscous slurry is obtained, usually with a viscosity or thickness equivalent to about 100 - 100,000 centipoises or more. This slurry usually comprises about 1/4 - 3/4 of During the addition of the silicate, the mixing continues at a comparatively low speed, eg with the maximum speed on the surface of the mixer being about 2 - 10 meters / second, but after formation one of the gelled high viscosity mixture or the viscous slurry is applied high shear force to the crutcher mixture, the shear rate being 20 - 50 meters / second or higher, and this shearing continues for a time which is normally about 1 - 20 minutes , preferably 2 - 10 minutes.

After lowering the viscosity of the mixture to a workable area, e.g. 10 - 50 centipoises, one returns to mixing at low speed which is allowed to continue for another 2 - 20 minutes preferably 5 - 10 minutes, the regular and gradual addition of silicate preferably in solution taking place during this time period. This secondary addition of silicate, especially when the silicate is a highly water-soluble sodium silicate with a Na 2 O: SiO 2 ratio of 1: 2 - 1: 3, e.g. about 1: 2.4, is not usually accompanied by further gelation to a thick mixture, but if so, the shearing procedures and subsequent additions are repeated until the desired thin "crutcher" mixture of the correct composition is obtained. the rest of the crutcher mixture, usually for a period of about 1 to 20 minutes, preferably 2 to 10 minutes.

After the crutcher mixture has been completely treated in the crutcher mixer, this mixture is atomized, preferably by pressing through a round nozzle with an inner diameter in the range of about 0.5 - 2 mm, with a pressure of about 10 50 kp / cm 2, into a spray tower, preferably a countercurrent spray tower, in which the drying air has a temperature of about 150 - 350 ° C. The tower can be about 8 - 15 meters high and about 2 - 4 meters in diameter and the product coming out of the tower has particle sizes which are substantially in the range of 0.095 - 3.36 mm (160 - 6 mesh according to US Sieve Standard) 7810337-1 23 and this product is sieved so that substantially all the particles fall within this interval or a narrower interval, e.g.

0.149 - 2.38 mm. Instead of using high pressure to atomize the particles through a nozzle, you can use a method with spinning discs for atomization or similar methods.

After the preparation of the base particles and when it does not contain any silicate, a particulate solid silicate is mixed with the base grains, such as aqueous sodium silicate, preferably of the type sold by the Philadelphia Quartz Company with a Na 2 O: SiO 2 ratio of 1: 2 or 1 : 2,4, which mixing takes place in an inclined cylinder or other such as Britesil, mixing and / or tumbling device, normally for a period of about 1 - 5 minutes, and nonionic detergent, in a liquid state and with a temperature within the range 20 DEG-70 DEG C., preferably 30 DEG-60 DEG C., are sprayed on the tumbling surfaces of the base grains (sometimes mixed with subsequently added particulate silicate).

The finely divided nonionic detergent spheres can be of any suitable size, but normally they are in the diameter range 0.5 - 3 mm, preferably 1 - 2 mm. The spray application of the nonionic detergent on the tumbling particles normally takes place for a period of from 1 to 20 minutes, preferably from 2 to 10 minutes. Although the base particles can be heated to remererur from 30 to eo ° C to scar promote the retention of normally pasty or solid nonionic detergent in liquid form, this is usually not done, as heating the detergent is sufficient to accomplish this, and for Normally liquid detergents do not require any heating. After the addition of the nonionic detergent is completed, other materials to be added afterwards can be applied, such as proteolytic enzyme and perfume. It is possible to add the proteolytic enzyme and any other powders first by simply mixing it or them with the base particles, which normally comprise for a period of 1-10 minutes, nonionic detergent, preferably 1-5 minutes, and then adding perfume for similar periods of time, preferably as a spray, the sprayed beads have sizes similar to those described with the nonionic detergent. The free-flowing spray-dried product, in which nonionic detergent has been absorbed, has a bulk density which is advantageously higher than the usual spray-dried detergent compositions and is therefore more suitable for use and requires less storage space.

Although in certain circumstances a limited proportion of phosphate, e.g. up to 10%, can be intentionally added to the present compositions, it is a feature or feature of the present invention that excellent cleaning ability, with little or no residual precipitation on washed garments, is obtained without the use of any phosphate. The combination of carbonate and bicarbonate in the base grains is a buffered mixture that keeps the pH of the product, at 0.07% concentration in washing water (1/4 cup in a 64-liter standard washing machine), in the range 8.5 - 11, preferably 9 - 10.5. The aforementioned pH value is ideal for the action of a possible enzyme contained in the product and thereby helps to improve the washing effect and stain removing effect of the detergent compositions. In addition, since during the spray drying operation there is a certain decomposition of bicarbonate to carbonate, carbon dioxide is released and locally existing areas in the product which may have higher alkalinity are neutralized, which helps to create a more homogeneous grain, which can help explain why the product is relatively compact, has a high bulk density and is highly absorbent. In addition, since the bicarbonate does not decompose to any significant extent in the crutcher mixer, but turns into carbonate during the spray drying, which is carried out for a short period of time, any other reactions with the base grain components which may take place at higher pH values are held back. in the "crutcher" mixer due to the buffering effect of the bicarbonate and, if they are timed reactions, they do not occur in any noticeable way during the spray drying despite the fact that the spray-dried base grains, if dissolved in water, usually have a slightly higher pH than the "crutcher" mixture.

When silicates are included in the described products, which have been spray-dried together with the base grains as described to the desired moisture content, the resulting detergent composition leaves little or no residue on the washed laundry, unlike the situation which can occur when a variety of silicates are added retrospectively or incorporated with zeolite-containing detergents in significant proportions, which silicates are similar to those used in the present invention.

As a result of the present manufacturing process, in which silicate is added to a "crutcher" mixture of water, carbonate and bicarbonate, optionally also together with fluorescent whitening agents, pigments and other non-surfactant constituents of the product (but not together with the nonionic detergent, proteolytic enzyme, perfume and other materials, which it is best to add afterwards) until a gel-like or highly viscous "crutcher" mixture is formed, after which the addition is stopped and the gel is destroyed or reduced. in the viscosity by applying shear forces, and the remainder of the silicate is added, the silicate and / or the zeolite do not cause any appreciable deposits or precipitates on the washed laundry. in the "crutcher" mixture together with other ingredients and although the "crutcher" mixture did not thicken on any note In a remarkable manner, the detergent composition produced precipitated or precipitated in a remarkable manner, often a residue or residue on the washed garments, especially if the amounts of silicate and zeolite were comparatively high. The reason for this disadvantage is not understood at present, but one theory is that the destruction of the silicate gel releases more moisture into the "crutcher" mixture to satisfactorily hydrate the zeolite, which prevents the formation of anhydrous zeolite and of combinations. of zeolite and silicate which are more likely to settle on the wash during washing.

The various advantages of the product and the process or method according to the invention are possible to achieve without additional materials or process costs and the use of phosphate is avoided.

Since the detergents used are nonionic, they are less 7810557-1% sensitive to the action of hardness-forming ions in the water and other contaminants and therefore the products are better detergents under a wider variety of conditions, including washing cold water. Even in water with high hardness, the compositions have a tendency to better disperse any insoluble carbonate that may form. Although carbonate in the discharged wash water that is discharged into drains and flows into lakes and other watercourses is a source of carbon, which is required for living organisms, carbonate is not as likely as phosphate to cause overgrowth on the groundwater. nutrients in lakes and watercourses in most circumstances, and carbonate is consequently more tolerable in lakes and other watercourses.

According to the third aspect or embodiment of the invention, a product similar to that of the second aspect or embodiment is prepared with the main difference that bicarbonate is not included in the preparation according to the third embodiment and that aqueous sodium silicate is included therein. Like the bicarbonate-containing product, the product according to this third embodiment is free-flowing and has a high bulk density and precipitates or deposits little residue on the washed material.

In accordance with the third aspect of the present invention there is provided a free flowing phosphate free particulate high performance detergent composition having a bulk density greater than 0.6 g / ml comprising a mixture of ion exchange zeolite and sodium carbonate granules and aqueous sodium silicate powder in which the proportions of said components are in the range 1: 0.1-1.5: 0.1-0.3, with about 0.2 - 1.0 or - 1.5 parts of nonionic detergent being absorbed in the granules, which weights are all calculated on an anhydrous basis. The nonionic detergent absorbed into the spray dried grains of zeolite and carbonate helps to keep the aqueous silicate in or on these grains. One method of preparing these compositions comprises spray drying an aqueous mixture of zeolite and carbonate in a proportion in the range of 1: 0, l-1.5, 7810337-1 after which the prepared grains are mixed with 0.1 - 0.3 parts of aqueous sodium silicate and in the mixture absorbs 0.2 - 1.5 or 0.2 - 1.0 parts of nonionic detergent in liquid form.

The nonionic detergents, zeolites, carbonate, fillers, auxiliary additives and water used are the same as those previously mentioned in the description of the second aspect of the invention. The alkali metal carbonate is usually particulate when added to an aqueous medium to form a crutcher mixture with the zeolite and the particle sizes of said carbonate are in the range 0.074 - 0.84 mm and are preferably in the range 0.74 - 0.149 mm . However, carbonate solutions can also be used. When solids are used, they should usually be anhydrous, but they can also be partially hydrated. The carbonate, usually substantially pure sodium carbonate, preferably has over 95% purity and has no significant proportion of bicarbonate present, such as kanamxß Uga in sodium sesquicarbonate, Wegscheider's salt or commercial products which are mixtures of carbonate and bicarbonate.

The water-soluble alkali metal silicate used is that usually referred to as an aqueous alkali metal silicate, preferably sodium silicate having a Na 2 O: SiO 2 ratio in the range 1: 1.5, 1: 2.5, preferably 1: 1, 8 - 1: 2 , 4, e.g. 1: 2. Although it is possible to add such silicate to the aqueous "crutcher" mixture together with the carbonate and the zeolite, but if such a procedure is followed in the preparation of the present detergent compositions, remarkable residual precipitates are sometimes noted on washed fabrics or laundry clothes should be avoided and it has been found that they are mainly avoided by subsequently adding aqueous alkali metal silicate, such a method of post-addition is normally used. Upon subsequent addition of the aqueous sodium silicate, preferably in particulate or powdered form, usually with particle sizes in the range 0.074 - 2.00 mm, e.g. 0.101 - 2.00 mm (150 - 10 mesh), the silicate is mixed with the spray-dried base grains of zeolite and carbonate before spraying the nonionic detergent in liquid form on tumbling surfaces to be sorbed by the spray-dried grains and in some extent of the aqueous silicate. Typical aqueous sodium silicates have shown the following sieve analyzes (for Britesil's H20 and H24): 55% pass through sieve no. 10 according to US Sieve Standard (2.00 mm mesh opening) and collected on sieve No. 48 (approximately 0.32 mm); 40% passes through sieve no. 48 (approximately 0.32 mm) and is collected on sieve no. 65 (approximately 0.23 mm); 4% passes through sieve No. 65 (about 0.23 mm) and is collected on sieve No. 100 (0.149 mm); and 3% pass through sieve no. 100 (0.149 mm) and collected on sieve No. 150 (approximately 0.101 mm).

The proportions of active ingredients in the final product must be in the range 1: 0.1-1.5: 0.1-0.3: 0.2-1.0 for zeolite: carbonate: silicate: nonionic detergent. These proportions are preferably 1: 0.2-1.0: 0.15-0.25: 0.3-0.8 in the order given. Indicated in percentages for these constituents plus water, these proportions correspond to 25 - 70% synthetic zeolite, 8 - 35% sodium carbonate, 5 - 15% aqueous sodium silicate, 15 - 25% nonionic detergent and 2 - 15% water. Normally 0 - 10% auxiliary additives are also included, e.g. 2 - 7%. These percentages are preferably 30-60% synthetic zeolite, 8-30% sodium carbonate, 7-12% aqueous sodium silicate, 17-23% nonionic detergent and 5-12% water. A particularly preferred formulation contains about 45% zeolite, 13% sodium carbonate, 8.1% aqueous sodium silicate, 20% nonionic detergent, 2% fluorescent whitening agent, 1.5% proteolytic enzyme, 0.2% pigment, 0.3%. % perfume and 9.9% water. The various ranges of auxiliary additives are normally about the same as those described with respect to the foregoing embodiments of the present invention. In the "crutcher" mixture, the percentages of the components are usually 20-60% zeolite, 5-30% carbonate and The particulate high-performance high-density detergent product of the present invention is usually in the form of free-flowing round granules, as for other spray-dried products, although the interior of the grains can be practically hollow.The particle sizes of the grains are normally in the range 0.095 - 3.36 mm (160 - 6 mesh), preferably 0.149 - - 2.38 mm, with less than 10%, preferably less than 5% and more preferably less than 1% of the product falls outside these ranges The bulk density of the finished detergent is normally at least 0.6 g / ml, preferably at least 0.65 g / ml and most preferably is the one in the range 0.65 - 0.85 g / ml eex. 0.71 - - 0.83 g / ml. The free-flowing ability of such products is excellent and is usually better than 70% of the free-flowing ability of sand with similar particle size, normally the free-flowing ability is 70-95% thereof and preferably 75-95% thereof.

Although the bulk density range 0.65 - 0.85 g / ml is preferred, it can be changed up and down, e.g. to 0.5 and 0.9 g / ml by changing the recipes and spray-drying techniques.

In the preparation of the invented detergent, it is important that a sorptive grain be prepared for absorption of nonionic detergent therein. Such sorption should be sufficient so that the nonionic detergent is introduced into the interior of the grains and therefore does not tend to cause agglomeration of the grains or cause poor dispersibility properties. Although some forms of sodium carbonate have been found to be gaseous sorbents for nonionic detergents (most are not), products tend to have remarkably high pH values prepared with the acceptable sorbent only as wash enhancers at least in quantities needed to produce compositions of the type which are acceptably detersive. Although this is the case, such products are not as free-flowing as those of the present invention. A sodium carbonate previously sold by Diamond Shamrock Corp. under the FlozaÅE brand) could, for example, absorb 20% nonionic detergent. Nevertheless, mixtures of Flozan nonionic detergent were not as free-flowing as the invented products. In addition, since carbonate has a tendency to precipitate calcium and magnesium ions and other alkaline earth metal ions and heavy metal ions as insoluble compounds, it can give rise to chalk precipitation in washed materials. When used in relatively small percentages according to the present invention in a spray-dried product together with synthetic zeolite of the type described, although both components can be considered individually to have a tendency to increase the residual problems on washed tissues, it nevertheless has It has been found that when the carbonate is used in the proportions described and together with the aqueous sodium silicate and nonionic detergent added thereto, the residual level is not such as to lead to remarks. In other words, when the zeolite and the carbonate are spray-dried together in the proportions described, the product, which comprises two materials, each of which can cause residual problems, turns out to be better than one would expect with respect to residual precipitation. The relatively small amount of carbonate contained also reduces the toxicity of the product and reduces the likelihood of esophageal rupture if the product is accidentally swallowed by infants or children.

In the preparation of the absorbent, yet comparatively high bulk density having spray-dried detergent bases, the spray-drying operation is carried out in a normal manner with only zeolite, carbonate, water and temperature-stable auxiliaries, such as fluorescent whitening agents and pigments, as normally included components. It is possible to spray dry a limited quantity of silicate, usually not more than 15% thereof, e.g. 5 - 12%, together with the rest of the "crutcher" mixture, but in general it is preferred to add aqueous sodium silicate afterwards. If the silicate is spray-dried together with the rest of the base composition, it is preferably a sodium silicate with a Na 2 O: SiO 2 ratio which is in the range 1: 2.0 - 1: 2.5, e.g. about 1: 2.4.

Whether or not the silicate is included in the crutcher mixture, this mixture normally comprises about 40-75% solids and about 25-60% water. The water content is preferably about 25-50 or -60%, the remainder of the mixture being non-surfactant solid materials. The procedures of mixing in the crutcher mixer and spray drying are usually the same as those of the other previously described aspect of the invention, except that bicarbonate is omitted. Remarkably, during treatment in the crutcher mixer, this mixture may be subjected to high shear as previously described in connection with the second aspect of the present invention.

The particle sizes of the finished product can be controlled by controlling the spray drying conditions and the particle sizes of the powders "mixed in afterwards with the spray-dried granules, but usually post-production sieving is also used to obtain the desired size ranges of 0.095 - 3.36 mm ( 160 - 6 mesh) or 0.149 - 2.38 mm.

The advantages of the present invention with respect to product and process technology are similar to those previously described in connection with the second aspect of the invention. The combination of zeolite and a relatively small amount of carbonate in combination with nonionic detergent and subsequently added aqueous sodium silicate (which can also be added after the addition of the nonionic detergent) results in a product having cleaning properties similar to those obtained. held with phosphate-containing detergent compositions. The relatively small amount of carbonate contained keeps the alkalinity of the product low and maintains the pH of the wash water at normal use concentrations in the range 8.5 - 11, preferably 9 - 10.5. The resulting product usually has a higher density than the comparable product according to the second aspect of the invention which includes bicarbonate. Although such a desirable effect can be attributed to a higher percentage of constituent zeolite, it is surprising that a product with such a high zeolite content with additional sodium carbonate, which is known to precipitate or deposit on laundry, does not produce unacceptable high residues in washed clothes. Although it has been taught that appreciable levels of silicate, either post-added or spray-dried simultaneously with other components of the detergent compositions, are likely to form zeolite-silicate or other residues or resurface on washed garments, in the present compositions and in the present case, it has been shown that any residue obtained is generally commercially acceptable and does not cause the product to be rejected by consumers.

The following examples illustrate the invention without limiting it.

Unless otherwise indicated, all parts are by weight and all temperatures are expressed in OC. EXAMPLE 1 Parts by weight Neodof®% 5-1 (condensation product of higher fatty alcohol and polyethylene oxide wherein the higher fat alcohol has on average about 14.5 carbon atoms and the ethylene oxide content is about 11 moles per mole, including the endethanol moiety ) Zeolite of type 4A [(na 2 O) 6- (Al 2 O 3) 6- (sio 2) 12-24 uzo] 20 Tetrasodium pyrophosphate 26 Sodium silicate (Na 2 O: SiO 2 = 1: 2.4) 3 Sodium carbonate 10 Sodium sulphate 16 Moisture 10 100 the composition is prepared by mixing together the zeolite, phosphate, carbonate and sulphate and tumbling the mixture, while spraying on its surface an aqueous solution of sodium silicate (about 40% solids), additional moisture and a melt of Neodol 45-II. The tumbling continues until round particles are formed of sufficient size so that during the screening which is then carried out a product is obtained which has particle sizes in the range 0.149-1.68.

The reinforced detergent obtained is tested in a laboratory washing machine of the Tergotometer type in a mixed dirt cleaning test, the product concentration being 0.15%, the washing water having a hardness of 150 ppm calculated as calcium carbonate (3: 2 molar ratio between calcium and magnesium hardness) and the water temperature is 49 ° C. The soiled fabrics used are fabric samples of nylon test fabric, cotton test fabric, cotton fabric stained with black dye (Empa 101), cotton fabric stained with clay and polyester-cotton fabric with permanent press and stained with clay. Final reflection readings, which are indicative of the whiteness of the tissues after washing with the experimental detergents, are as follows: 7810337-1 34 Test fabric Final reflection (Rd) Nylon 70.0 Cotton 42.3 Empa 101 - 33.5 Clay on cotton 72.0 Clay on permanent pressure sample 76.6 When a comparable product is prepared, with the only changes in the preparation that tetrasodium pyrophosphate is replaced by an "equivalent" (based on the phosphorus content) proportion (24 parts) pentasodium tripolyphosphate and that the sodium sulphate content is increased from 16 to 18 parts the test results obtained (Rd) 61.3 (nylon); 41.6 (cotton1l); 33.9 (Empa 101); 69.2 (clay on cotton samples); and 75.8 (clay on samples with permanent pressure).

Thus, it is quite obvious that superior cleaning is obtained with the "experimental" product on nylon and superior removal of black dye stains (Empa 101) is also obtained, while equal or better results are obtained in the other three cases than when tripolyphosphate is used. Corresponding Rd values for a commercial detergent containing 1% Neodol 45-1, 20% sodium linear tridecylbenzenesulfonate (LAS), 24% pentasodium tripolyphosphate, 7% sodium silicate (Na 10% sodium carbonate, 28% sodium sulfate and 10% moisture, are as follows: 64.5 (nylon); 45.4 (cotton); 36.0 (Empa 101); 67.6 (clay on cotton sample); and 71.0 (clay on tissue with permanent pressure). These results show that the experimental product is superior to the commercial product in cleaning nylon, removing clay soils from cotton and removing clay soils from tissue with permanent pressure. It seems to be roughly equivalent to the commercial product in removing stains of black dye and cleaning test tissue of cotton.

When in the above experimental recipe instead of a type 4A zeolite, as described, which is hydrated to about 90%, taking into account that 27 moles of water in the hydrate molecule corresponds to 10% hydration, the corresponding 100% hydrated the zeolite, the 80% hydrated zeolite and the 50% hydrated zeolite of the same formula except for the content of hydrating water, similarly washable detergent detergent compositions are obtained. However, the zeolites with lower degrees of hydration, although capable of absorbing more moisture and thereby becoming more free-flowing, may have a tendency to disperse more slowly in the wash water and may sometimes form lumpy products due to uneven application of moisture. Although usually the anhydrous form of the zeolite is not used, such a zeolite can be used in exchange for the other zeolites previously described herein, when well distributed throughout the composition, is finely divided and circulated satisfactorily in the wash water, when it is added to it in the fortified detergent.

In addition to the differently hydrated type 4A zeolite, the corresponding type X and Y zeolites can also be used, either as a complete or partial replacement, e.g. 10%, 50% and 90%, of the zeolite and mixtures of type 4A, other zeolites of type A, and zeolites of types X and Y can be used, the resulting products being free-flowing and effective high-performance detergents in certain aspects of the invention. one can at least partially utilize the corresponding potassium zeolites, such as up to 25% of the total zeolite content of the product.

Other suitable zeolites that can be used for replacement purposes are the crystalline and amorphous zeolites.

In the above recipe, instead of Neodol 45-111, Neodol 25-7 and / or Alfonic 1618-65 or other of the solid nonionic detergents mentioned previously can be used, and the product obtained is a very satisfactory high-performance detergent composition. However, when normally liquid nonionic detergents are used in place of those which are solid at room temperature, the product may be less free flowing than desired and consequently the use of such nonionic detergents is minimized or reduced to a minimum.

When the sodium carbonate in the previously described preparations is omitted, the cleaning ability of the composition is reduced, but the product 7810357-1 36 is still useful. in a preferred embodiment of the invention, the described experimental product or the experimental products are prepared by spray-drying the components according to the given recipe, with the exception of 13 parts by weight of Neodol 45-II, in the form of an aqueous "crutcher" mixture (50% solid material), the spray drying being carried out at a pressure of 30 kp / in heated drying air (with a temperature of 300 ° C) in a counter-spraying tower to form a product containing the detected 10% moisture, on which product the rest of the nonionic detergent is sprayed as a melt, while the particles are tumbled. The particles are sieved and those collected have a size in the range 0.149 - 1.68 mm. By following a second different and preferred method, 13% of the nonionic detergent and 10% of the zeolite and 7% of the nonionic detergent are premixed with the zeolite in a crutcher mixture, with the moisture content previously mentioned. tumbling cylinder, after which a zeolite thus treated is mechanically mixed by tumbling with the spray-dried residue of the composition except for the remainder of the nonionic detergent, which is melted and sprayed on the surface of the tumbling mixture of the remainder of the preparation, after which the desired particle sizes (O , l49 - 1.68 mm) is taken out for packaging purposes. The spray-dried and subsequently mixed products described herein are excellent high-performance detergents which are free-flowing and have the desired cleaning ability which is superior to that obtained with the detergents based on pentasodium tripolyphosphate as phosphate builder salt. The presence of the small quantity of the desired type of sodium silicate makes the composition anticorrosive to aluminum and other metals, does not adversely affect the spray drying operation (larger quantities of silicate sometimes result in the formation of a sticky product) and does not cause remarkable precipitation of white powder on the wash ( which powder can sometimes be obtained when large quantities of silicate are used, probably due to some interaction with zeolite). 7810337-1 37 EXAMPLE 2 Parts by weight Neodol 23-6.5 (Shell Chemical Company) * 20.0 Molecular silzeolite 4A, crystalline, final particle size 4-8 microns (Union Carbide Corporation) ** 25.0 Na2co3 18.5 NaHCO3 14.0 Sodium silicate (Na 2 O: SiO 2 = 1: 2.4) 10.0 Tinopal® SBM, fluorescent bleach 2.0 Proteolytic enzyme 1.5 Ultramarine blue, pigment 0.2 Perfume 0.3 Water (including hydration water of the zeolite, etc.) 8, 100.0 * Condensation product of higher-fat alcohol with an average of 12 to 13 carbon atoms with about 6.5 moles of ethylene oxide / mol.

** Anhydrous bass.

A free-flowing, high bulk density, particulate detergent composition is prepared from the above recipe and essentially globular particles are obtained, 99% of which have sizes (usually considered as diameters) ranging from 0.149 to 2.38 mm. The product has a bulk density of 0.72 g / ml and flows at a rate of about 77% of this rate for dry sand of similar particle size, which sand is standard for comparison purposes. The product is an excellent high performance synthetic organic detergent, which is useful for washing in both hot and cold water of both synthetic and natural fiber textiles and it does not leave remarkable residues on these textiles, as is often observed after washing with other synthetic detergent compositions, in which essential proportions of zeolite (a water-insoluble inorganic builder) and silicate were used together.

The product is prepared by using a mixer for synthetic 7s1o3s7-1 w detergent or for soap, which mixer is called a "crutcher" mixer and has a temperature of 60 ° C (the water is initially heated and the heat of the "crutcher" mixer is maintained to reach and maintain such a temperature), mixes zeolite, sodium carbonate and sodium bicarbonate, plus stable auxiliaries such as pigments and bleaches. The parts by weight used are 25 of anhydrous zeolite, 11 of sodium carbonate, 22 of sodium bicarbonate, 0.2 of the pigment, 2 of the white agent and 55 of deionized water.

Alternatively, the deionized water is in some cases exchanged for tap water with low hardness, less than 50 ppm calculated as calcium carbonate. After about 5 to 10 minutes of mixing, an aqueous sodium silicate solution containing 40% solids is added to the crutcher mixture. After about 12 parts of this solution have been mixed, which takes about 4 minutes, the slurry becomes very viscous, with a viscosity or of a thickness equivalent to a viscosity of about 1,000 centipoises or more. During this mixing and in the mixing of the water, the carbonate, the bicarbonate, the zeolite, the pigment and the fluorescent whitening agent, before mixing the sodium silicate solution, the mixer is set at a comparatively low speed, the mixer having a maximum speed on the mixing surface of about 5 m / sec. . After the formation of a thickened mixture, high shear is applied for a period of about 6 minutes, the shear rate being about 35 m / sec, to break up the gel and thin out the slurry, after which the rest of the silicate mixture is gradually added using the lower mixing speed previously used. After the addition of this residue is completed, which takes about 8 minutes, the "crutcher" mixture is spray-dried in a conventional countercurrent spray tower, which is about 10 meters high and 3 meters in diameter, by pumping the mixture with a pressure of about 25 kp / cm 2 through an opening of about 1 mm in diameter into the drying air (with a temperature of about 300 ° C at the inlet and 110 ° C at the outlet) to form a product which is substantially in the range of 0.095 - 3 36 mm (160 - 6 mesh according to the US Sieve Series), which product is cooled to approximately room temperature and sieved so that essentially all (over 99%) fall within this size range. Alternatively, the screening is carried out so that particle sizes falling within the narrower range of 0.149 - 2.38 mm are obtained. In both cases, the base grains obtained have a high bulk density, about 0.6 g / ml, and are free-flowing, this free-flowing capacity being about 80% or more of that of dry sand of comparable particle size.

On the base grains which have a size of 0.095 - 3.36 mm (160 - 6 mesh) and which are present in an inclined cylinder mixer, spray 20 parts of Neodol 23-6.5 in a liquid state at a temperature of about 30 ° C. The particles on which this component Neodol 23-6.5 is sprayed as a mist with diameters on the droplets of about 2 mm initially have a temperature of about 30 ° C (when normally a nonionic detergent is used, the temperature of the detergent is 40 - 50 ° C and the temperature of the grains can be similarly raised to prevent immediate solidification of the sprayed nonionic detergent and to promote the penetration of this detergent into the inner pores of the base grains). This spraying is carried out within a time of about 8 minutes, after which the perfume is sprayed on and the proteolytic enzyme powder with a particle size between 0.149 and 0.250 mm is dusted on the surfaces of the particles still present in the mixing cylinder, each procedure taking about 3 minutes. The product is allowed to cool to 30 ° C after absorption of the nonionic detergent (if it has a higher temperature) to avoid unnecessary loss of perfume components by evaporation.

The finished product, which is sieved to a particle size in the range 0.149 - 2.38 mm, exhibits the desired high bulk density and very good spreadability properties and is packaged and stored ready for distribution. When tested, the product is found to be a satisfactory high performance detergent which is useful for washing in both hot and cold water and which surprisingly leaves little or no residue of zeolite and / or silicate or other materials on the washed tissues. The product remains free-flowing during storage. It does not coagulate in any remarkable way, nor does it produce poor dispersibility properties. The pH of a 0.07% solution thereof in the washing water is about 9.5, which is an ideal pH for proteolytic enzymatic action, which assists the detergent composition in the cleaning and removal of stains from washed tissues of both synthetic and (nylon, polyester and natural-synthetic blends with permanent pressure) as natural fabrics (cotton).

When the "crutcher" mixture, instead of using the spray-drying process, is prepared at a temperature within the higher part of the given range, e.g. about 85 ° C, the water content is kept to a minimum for the mixture and spray cooling is used to provide crystalline hydrates of the hydratable components of the "crutcher" mixture, thereby providing base particles which are treated with nonionic detergent in the manner previously described. However, the absorption of the nonionic detergent is not so good and the particles, which contain more moisture and more unabsorbed nonionic detergent, have poorer free-flowing properties than the preferred product previously described. in another variation of the above experiment the silicate is omitted from the "crutcher" mixture and is subsequently added as aqueous sodium silicate (Britesil), either before or after the addition of the nonionic detergent (preferably), whereby a product is obtained which, while constituting a good high performance detergent, having the high bulk density, in the range of 0.65 - 0.8 g / ml, and being sufficiently free flowing to be commercially acceptable, may not be as good as that of the example in little or no residue on washed tissues. Although the residue deposited or precipitated may be acceptable in many cases, especially when the laundry clothes are not dark colored so that the more light colored residue easily appears, the residual precipitation is still remarkable in many cases and is preferably completely avoided.

In a variation of the manufacturing process in the main test according to this example, the mixing operations are carried out using two different vertical mixers, one of which is either of the vane type or screw type and operates at comparatively low speeds and of which the other is of a disc design in opposite directions rotating discs with shear action and operate 7810337-1 41 at high speeds. One or the other of the mixing elements is used at a time, whereby what is not used is removed from the mixer. The products produced using the combination of mixers instead of the same mixer with different speeds, have essentially the same properties as the product described above, but due to the increased shear efficiency of one mixer, the treatment is faster. , whereby a saving of 2 to 6 minutes is obtained per batch.

Although it is common, as stated above in the main part of this example, to subsequently add the nonionic detergent to the granules shortly after the preparation and also to subsequently add any other components of the product which are not in the spray-dried base granules, this can also be done after aging of the base grains for periods of time from 20 minutes to several days without loss of their absorbency. In such cases it is desirable to heat the granules before the application of the nonionic detergent, but by the correct choice of type of nonionic detergent with respect to melting point such heating can be avoided.

EXAMPLE 3 Products according to the recipe given in Example 2 are prepared by utilizing different initial proportions between sodium carbonate and sodium bicarbonate and modifying the conditions of the drying tower accordingly to thereby cause more or less decomposition of the sodium bicarbonate, e.g. 10 - 70%.

For example, instead of using 22 parts of sodium bicarbonate and 11 parts of sodium carbonate, 18 parts of the bicarbonate and 15 parts of the carbonate can be used, while changing the tower conditions (temperatures, residence time) to reduce the decomposition of the bicarbonate. Of course you can start with more bicarbonate, such as 25 parts, and less carbonate, e.g. 8 parts, and take advantage of increased residence times in the tower and higher temperatures in the tower to cause more extensive decomposition of the bicarbonate. In both these cases, the finished product will have substantially the same properties as the product according to a preferred embodiment of the invention described in Example 2.

Such a product is also obtained when, instead of utilizing the separate carbonate and bicarbonate components, the starting material used is one in which the two components are mixed, as is the case in the Snowlite products mentioned. Parts of the carbonate and bicarbonate contents of the nenter which previously or all of these contents may come from commercially available products, such as Snowlite products, Wegscheiderite, sodium, etc. a component of the crutcher mixture.

EXAMPLE 4 A crutcher preparation for a product with a comparatively high zeolite content is made by mixing together 22.0 parts of sodium-aluminum silinai Wzeolzzxyp QR. calcined soda (natural), 14.2 parts of sodium silicate solution (47.5% solids, Na2O: SiO2 ratio = 1: 2.4) 0.1 parts of ultramarine bleach fl 1.3 parts of Tinopal SBM COnc ,, 39.6 parts of water, wherein wetting and corrosion are increased in such quantity and proportion (qs) as to form a "crutcher" mixture containing 48.0% solids. The base composition described is spray dried according to the method set forth in Example 2, the moisture loss being 47.8% and the loss from the decomposition of bicarbonate to carbonate is 2.5% so that the yield is 49.7% The resulting product, which has particle sizes similar to those described for the products of Example 2, is subsequently mixed with Neodol 23-6.5, proteolytic enzyme (Maxazyme P-375 ) and perfume in the proportions 78.4, 20.0, 1.3 and 0.3 and the result is a product containing 26.9% (anhydrous base) zeolite, 10.6 silicate in solid form, 13.4% umcarbonate 2% sodium bicarbonate (23.9% was added), l8.7% sodium ( 12% was added), 20% nonionic detergent, 1.3% enzyme, fluorescent bleach, 0.2% pigment, 6.6% water and 0.3% perfume. The weight of a cup is l55 g (the cup holds 240 ml), The spreadability is similar which indicates a bulk density of 0.65 g / ml. that of the product according to Example 2 and the product is similarly useful as a high performance detergent having properties similar to those described for the product of said example. EXAMPLE 5 Parts by weight of Neodol 23-6.5 (Shell Chemical Company) * 20.0 aylalkylsilzeolite 4A, crystalline, final particle size 4-8 microns (Union Carbide Corp.) ** 45.0 Na2CO3 13.0 Aqueous sodium silicate, Britesil, manufactured by Philadelphia Quarts Company (Na2O: SiO2 = 1: 2.4) ** 8.1 Tinopal SBM, fluorescent bleach 2.0 Proteolytic enzyme l, Ultramarine blue, pigment 0, Perfume 0, Water (including hydration water of the zeolite, the silicate, etc.) 9.9 100.0 ** Anhydrous base A free-flowing high bulk density having a particulate detergent composition is prepared from the above formulation and substantially globular particles are obtained, 99% of which are of sizes (usually considered as diameters) which are in the range 0.149 - 2.38 mm. The product has a bulk density of 0.79 g / ml and flows at a rate of about 91% of that of dry sand of similar particle size, which is standard for comparative purposes. The product is an excellent high-performance synthetic organic detergent, which is useful for washing in both hot and cold water of both synthetic and natural textile fibers and it leaves no remarkable residue on such textiles, as can often be observed after washing with other synthetic detergent compositions in what essential proportions of zeolite as insoluble inorganic detergent builder and silicate were used together, when the compositions 7810357-1 M were used in concentrations of 0.05 - 0.15%, e.g. 0.07%, in wash water with medium hardness, e.g. 75 - 125 ppm as CaCO3.

The product is prepared by mixing in a synthetic detergent or soap mixer ("crutcher" mixer) at a temperature of 60 ° C (the water is initially heated and the heat of the mixer is maintained to reach and maintain such a temperature). sodium carbonate, plus stable adjuvants such as pigments and bleaches. The parts by weight used are 55 of the zeolite (hydrated), equal to 45 parts of anhydrous zeolite, 13 of sodium carbonate, 0.2 of the pigment, 2 of the white matter and 50 of deionized water (plus 10 parts of water in the zeolite).

Alternatively, the deionized water can in some cases be replaced with low hardness tap water, less than 50 ppm calculated as calcium carbonate. After about 20 minutes of mixing at a temperature of about 60 ° C, the "crutcher" mixture is spray dried in a conventional countercurrent spray tower, which is about 10 meters high and 3 meters in diameter, by pumping the mixture at a pressure of about 25 ° C. kp / cm 2 through an opening of about 1 mm in diameter into drying air (with a temperature of about: 300 ° C at the inlet and 110 ° C at the outlet) to form a product with a moisture content of about 14% (which can be removed at 10 ° C for 5 minutes), which product is usually substantially above 80% in the range of 0.095 - 3.36 mm (160 - 6 mesh according to the US Sieve Series), the product being cooled to about room temperature (if it is above this) and aimed so that essentially the entire product (over 99%) falls within this size range. Alternatively, the screening is performed to particle sizes in the narrower range 0.149 - 2.38 mm. In both cases, base grains are produced from the detergent composition having a high Skijymåenâitêtf of about 0.6 g / ml, which grains are free-flowing with such a free-flowing ability that it is about 80% or more of that of sand of comparable particle size.

With the base grains, about 10 parts of aqueous sodium silicate (8.1 parts of anhydrous silicate) are mixed with particle sizes in the range of 0.149 - 2.00 mm (to result in the prescription amount of silicate in the product) and after about 5 minutes 7810337-1 mixture is sprayed on the mixture 20 parts of Neodol 23-6.5 l liquid state with a temperature of about 35 ° C. The particles on which Neodol 23-6.5 is sprayed as a liquid mist with diameters of the droplets of about 2 mm have an initial room temperature (about 25 ° C). The spraying is carried out within a period of about 8 minutes, after which the product is perfumed by spraying and the proteolytic enzyme powder, with a particle size between 0.149 - 0.250 mm, is dusted on the surfaces of the particles still present in the mixing cylinder, each of these procedures taking about 3 minutes. The product is then allowed to cool to 30 ° C (if it has a higher temperature) to prevent loss of perfume components by evaporation.

The finished product, which is sieved to a size of 0.149 - 2.38 mm, has the desired high bulk density and very good free-flowing properties and is packaged and stored ready for distribution.

When the product is tested, it turns out to be a satisfactory high-performance detergent, which is useful for washing in both hot and cold water, especially at low concentrations, eg 0.07% in the washing water, and surprisingly leaves the product little or no visible residue of zeolite and / or silicate or other materials on the washed tissues. The product remains free-flowing during storage. It does not bake itself in any remarkable way, nor does it evoke poor dispersibility properties. The pH of a 0.15% solution thereof in wash water is about 9.8 and and the pH of a 0.07% solution is about 9.5, which pH values are ideal for proteolytic enzymatic action. , which assists the detergent composition in cleaning and removing stains from washed fabrics, whether these are synthetic (nylon, polyester and blends of natural and synthetic materials with permanent pressure) or natural fabrics (cotton).

When the silicate is incorporated into the crutcher mixture instead of being added afterwards (an aqueous solution containing 40% solids and having a Na 2 O: SiO 2 ratio of about 1: 2.4 is used instead of particulate water - further silicate) a further mixture is carried out in the mixer for a period of 5 minutes to mix the silicate with the rest of the crutcher mixture (it is added to the carbonate and the water before the addition of the zeolite and the water content of the silicate solution is taken into account of the amount of water to be added to the mixer). The product obtained is a good high-performance detergent with a high bulk density and is sufficiently free-flowing to be commercially acceptable, but it is not considered as good as the product obtained in the example previously given.

In another variation of the experiment, the aqueous sodium silicate is mixed in powder form with the remainder of the product, to which the silicate at least partially adheres after the nonionic detergent is sprayed onto this product. The resulting composition, although acceptable, is not as good as that in which the particulate aqueous sodium silicate is mixed with the zeolite first, prior to spraying the nonionic detergent onto the mixture. The free-flowing properties are not so good, some caking is noted during storage and some separation or separation in the product occurs.

Instead of using the inclined cylinder for mixing and spraying purposes, double-jacketed mixers of type V or Patterson Kelley are used instead, whereby equivalent products are obtained.

Although it is preferred, as indicated in the previous part of this example, to subsequently add the nonionic detergent to the granules shortly after preparation and also to subsequently add any other components of the product which are not included in the spray-dried base granules, this may also performed after aging the base grains for periods of time from 20 minutes to several days, without loss of their absorbent abilities. In such cases, it may be desirable to heat the granules prior to the application of the nonionic detergent, but by proper selection of the nonionic detergent type with respect to melting point, such heating can be avoided. ..._.___._ .. .- I _._ M 7810337-1 EXAMPLE 6 When the crystalline zeolite 4A in the procedures and products of Example 5 is replaced by the corresponding amorphous material, which has a final particle size (diameter ) in the range of 0.01 - 0.05 microns or when the "holes" in the zeolite increase or decrease, while the zeolite is still good for capturing hardness-forming ions, e.g. 3 - 6 Å, the obtained composition has substantially the same free-flowing ability and bulk density properties as those obtained for the product according to Example 5, and the obtained product is an excellent high-performance detergent which leaves no residue on washed clothes and has sometimes empty superior properties with respect to free-flowing ability and absence of residue compared to the crystalline product. This is also true, but to an even lesser extent, when 50:50 mixtures of amorphous zeolite and crystalline zeolite are used. When the type X zeolites are used instead of type A, such effects are also obtained.

In the same way, useful products can be obtained when type Y zeolites are used and other equivalents thereof, although these products are not as good as those comprising the type A and / or X zeolites.

The products of this example and of Example 5 are also useful when the silicate is partially incorporated into the crutcher mixer and partially into the inclined cylinder mixer, e.g. half in each, preferably with the first part constituting silicate with a Na 2 O: SiO 2 ratio of 1: 2.4 and the latter part constituting aqueous sodium silicate with a ratio of 1: 2. Alternatively, the silicate and co-additives may be omitted, although this is not preferred.

In addition to varying the type of zeolite that is included, you can change the types of silicates and nonionic detergent, as well as you can do with the various auxiliary additives. Thus, instead of using the aqueous silicate with an Na 2 O: SiO 2 ratio of 1: 2 in the experiment of Example 5, such a ratio may be 11.8 or 1: 2.2 and the products obtained are 7810337-148 still similar to those previously described. Instead of using Neodol 23-6.5, Neodol 25-7 and Neodol 45-II, you can use mixtures of these materials with 2 or 3 components in equal proportions. Instead of Tinopal SBM, you can use other of the previously mentioned fluorescent whitening agents or the whitening agent can be omitted altogether. In the latter case, the product obtained has substantially the same detersive and physical properties, although the desirable whitening of the laundry is markedly reduced in the absence of the fluorescent compound.

According to other variations of the procedure and products of Example 5, the proteolytic enzyme and ultramarine blue are omitted from the recipe. Alternatively, the dye material is used in greater proportion to dye some product particles, while others are unstained and the grains of both types are mixed to form a spotted appearance.

In addition to the various components listed, other components are also included, e.g. inert fillers such as sodium sulfate, anti-precipitating agents such as sodium carboxymethylcellulose, antibacterial agents such as tetrabromosalicylanilide, salts which make the laundry easy to care for (and which enhance the washing effect) such as borax, and bleaching materials such as sodium perborate. The stable materials are usually added preferably in the "crutcher" mixer, while the other materials are added afterwards, either before or after the spraying of the nonionic detergent. When such materials are included in the described compositions, for example 5% borax, 5% sodium sulfate, 0.5% sodium carboxymethylcellulose, 0.1% antibacterial compound and 10% sodium perborate, the recipe of the product is modified accordingly, preferably by proportional reductions in zeolite. , carbonate and silicate contents.

Instead of the sodium salts of the various components mentioned, the corresponding potassium or other suitable soluble salts may be used, preferably alkali metal salts, either as a whole substitute or as a partial substitute, provided that the properties obtained on the products are acceptable and within the specified intervals. According to a suitable embodiment of the invention, in addition to those stated in the appended claims, the detergent comprises about 15% of higher-fat alcohol-polyoxyethylene ethanol, wherein the higher-fat alcohol has on average about 14.5 carbon atoms and the polyoxyethylene group, including the endethanol then, has about 11 moles of ethylene oxide per mole, and the detergent comprises about 20% synthetic zeolite builder which is a type 4A crystalline zeolite having the molecular formula (Na 2 O) 6- (Al 2 O 3) 6 '(SiO 2) 12-27H % tetrasodium pyrophosphate, about 3% sodium silicate with a Na 2 O: SiO 2 ratio of about 1: 2.4, about 10% sodium carbonate, about 15% sodium sulfate and about 10% moisture.

In another such suitable embodiment of the invented detergent, the ratio of bicarbonate to carbonate is in the range 1: 2 - 2: 1, the zeolite is a type A zeolite with crystalline, amorphous structure or crystalline and amorphous structure in a mixture and the nonionic detergent is a condensate of higher fat alcohol and polyethylene oxide, in which the higher fat alcohol has 10 to 18 carbon atoms and the polyethylene oxide has 3 to 30 moles of ethylene oxide per mole of higher fat alcohol, the proportions of zeolite, carbonate , bicarbonate, water and nonionic detergent are in the ranges 15 - 40%, 10 - 25%, 8 - 22%, 2 - 10% and 15 - 25% respectively.

A detergent according to a further suitable embodiment of the invention has a bulk density in the range 0.65 - 0.85 g / ml, a grain form with particle sizes in the range 0.095 - 3.36 mm (160 - 6 mesh according to US Sieve Series), which detergent contains sodium silicate with a Na2O: SiO2 ratio of about 1: 2.4, the zeolite having the formula (Na2o) 6- (Al2O3) 6- (sio2) 12-24-wrzo and w is 20 - 27, and the detergent contains about 20% nonionic detergent, 25% zeolite, 20% sodium carbonate, 14% sodium bicarbonate, 10% sodium silicate, 2% fluorescent white, ._ ..,., - ..., ... i ...... 1_ 78 agents, 1.5% proteolytic enzyme, 0.2% pigment, 0.3% perfume and 8% water.

A detergent according to yet another suitable embodiment of the invention has a bulk density in the range of 0.65 - 0.85 g / ml and a granule shape with particle sizes in the range of 0.095 - 3.36 mm (160 - 6 mesh according to US Sieve Series), wherein the detergent contains aqueous sodium silicate with particle sizes in the range 0.074 - 0.149, which sodium silicate adheres to the other components of the detergent, the zeolite having the formula wherein w is about 20 - 27, and the nonionic detergent constituting a condensation product of a higher fat alcohol with 12 - 18 carbon atoms and 5-12 moles of ethylene oxide per mole, said silicate having a Na 2 O: SiO 2 ratio of about 1: 2, and the detergent contains about 20% nonionic detergent, 45% zeolite, 13% sodium carbonate, 8.1% aqueous sodium silicate, 2% fluorescent bleach, 1.5% proteolytic enzyme, 0.2% pigment, 0.3% perfume and 9.9% water.

A suitable method of preparing the detergent composition of the invention, in addition to those set forth in the claims, utilizes an ion exchange zeolite which is a synthetic sodium aluminosilicate, a nonionic detergent which is a condensation product between higher fatty alcohol and polyethylene oxide, wherein the higher fatty alcohol has 18 carbon atoms and the polyethylene oxide have 3 to 30 moles of ethylene oxide per mole of higher fat alcohol, the aqueous mixture being spray dried comprising 10 to 35% synthetic zeolite, 5 to 20% sodium carbonate, 10 to 30% sodium bicarbonate and 25 to 60% water and the proportion between bicarbonate and carbonate is in the range 1: 1 - 4: 1 in the aqueous mixture and in the range 1: 2 - 2: 1 in the spray dried product.

According to a further suitable method, a detergent having a bulk density in the range of 0.65 - 0.85 g / ml is prepared, the crutcher mixture comprising 2 - 15% water-soluble sodium silicate having a Na 2 O: SiO 2 ratio in the range of 1 : 2 - 1: 3 M 7810537-1 so that the product contains 3 - 20% thereof, the zeolite is a type A zeolite with crystalline, amorphous or mixed crystalline and amorphous structure and the nonionic detergent is a condensation product of a higher fatty alcohol having 12 to 15 carbon atoms and 5 to 12 moles of ethylene oxide per mole, the aqueous mixture of zeolite, carbonate, bicarbonate, silicate and water being a "crutcher" mixture prepared by preparing a slurry of water, sodium carbonate and sodium bicarbonate, after which sodium silicate is mixed with this mixture until a gel is formed, which gel is subjected to shear to lower its viscosity, after which the mixture thus treated is mixed with additional silicate f to obtain the desired concentration thereof.

According to a further suitable embodiment of the method for preparing the detergent according to the present invention, the zeolite is crystalline and has the formula wherein w is about 15 - 27, the mixing being carried out in a "crutcher" mixer at a temperature in the range of about 20 - 70 ° C. the spray drying is carried out in a spray tower by drying air with a temperature in the range of about 150 - 350 ° C, the "crutcher" mixture is atomized by pressing through a round nozzle with an inner diameter in the range of about 0.5 - 2 mm with a pressure of about 10 - 50 kp / cm 2, the spray-dried product is sieved to sizes in the range 0.095 - 3.36 mm (160 - 6 mesh according to US Sieve Series), the nonionic detergent being a condensation product of a higher-fat alcohol with 12 13 carbon atoms and about 6.5 moles of ethylene oxide per mole, which nonionic detergent is applied to the spray dried particles as they are tumbled in a tumbling cylinder by the detergent being pray in a liquid state with a temperature in the range of 20 - 70 ° C on the moving surfaces of the spray dried particles to form particles having sizes in the range of 0.095 - 3.36 mm (160 - 6 mesh).

In another suitable method of preparing detergent according to the present invention, the ion exchange zeolite is a synthetic sodium aluminosilicate, the nonionic detergent is a higher fat alcohol-polyethylene oxide condensate in which the higher fat alcohol has 10 to 18 carbon atoms and polyethylene 3 - 30 moles of ethylene oxide per mole of higher-fat alcohol, the aqueous mixture being spray-dried comprising 20 - 60% synthetic zeolite, 5 - 30% sodium carbonate and 25 - 60% water, and the ratio between zeolite and carbonate is in the range 1: 0. 2 - 1.0 in the aqueous mixture and in the final product.

In a further method of preparing detergent according to the present invention, a product having a bulk density in the range 0.65 - 0.85 g / ml is provided, the zeolite being a type A zeolite with crystalline, amorphous or mixed crystalline and amorphous structure, the nonionic detergent is a condensation product of a higher-fat alcohol having 12 to 15 carbon atoms and 5 to 12 moles of ethylene oxide per mole, the aqueous sodium silicate has a Na 2 O: SiO 2 ratio in the range 1: 1,8 - 2,4, which aqueous sodium silicate is mixed with the spray-dried base grains in such a proportion that the final product contains 5 - 151 thereof and the nonionic detergent is sprayed on the mixture of the base grains and the aqueous sodium silicate is present in such a proportion that the final product contains 15 - 25% thereof.

According to a further suitable method of preparing detergent of the present invention, a zeolite is used which is crystalline and has the formula (Na 2 O) 6: (Al 2 O 3) 6 '(SiO 2) 12-24'wH 2 O v wherein w is about 15-27, the mixture being carried out in a crutcher mixer at a temperature in the range of about 20 - 70 ° C, the spray drying is carried out in a spray tower by drying air with a temperature in the range of about 150 - 350 ° C, the "crutcher" mixture is atomized by pressing through a round nozzle with inner diameter in the range of about 0.5 - 2 mm with a pressure of about 10 - 50 kp / cmz, Var'ss 7810337-1 after the spray-dried product is sieved to sizes in the range 0.095 - 3 , 36 mm (160 - 6 mesh according to US Sieve Series), the nonionic detergent being a condensation product of a higher fat alcohol having 12 to 13 carbon atoms and about 6.5 moles of ethylene oxide per mole and being added to the mixture of particulate aqueous silicate and sp ray-dried particles, when this mixture is tumbled in a tumbling cylinder, by spraying the nonionic detergent in a liquid state with a temperature in the range of 20 - 70oC on the moving surfaces of the mixture to form particles in sizes in the range of 0.095 - 3, 36 mm.

The invention has been described with reference to illustrative examples and descriptions of these examples, but the invention should not be construed as limited to such examples, as it will be apparent that those skilled in the art, after having read the present description, will be able to utilize replacement means and equivalent means and make a number of different modifications within the scope of the invention.

Claims (12)

781Û337-1 M P_a t e n t k r a v A phosphate-free, free-flowing, particulate, high-performance detergent which comprises a water-soluble nonionic detergent, a calcium ion-exchange zeolite of the formula (Na 2 O) x - (Al 2 O 3) y - (sio 2) z - w. H 2 O wherein when x is 1, y is from 0.8 to 1.2, z is from 1.5 to 3.5 and w is from 0 to 9, and either sodium carbonate or sodium silicate having a Na 2 O 1 SiO 2 molar ratio in the range 1: 0.66 to 1: 4, characterized in that the detergent has a bulk density of more than 0.6 g / ml and comprises a water-soluble nonionic δ detergent absorbed on spray-dried granules consisting of a mixture of said zeolite and either sodium carbonate or a mixture of sodium carbonate and sodium bicarbonate J a weight ratio in the range 3: 8 - 5: 1, said spray dried grains containing flour, 1n 2 and 15% by weight of water and so that the weight proportions between zeolite and sodium carbonate are between 1: 0, 1 and 1: 1, 5, or so that the weight proportions between zeolite and sodium carbonate together with sodium lumbicarbonate are between 1: 0.5 and 1: 3.6, and in which grains the proportions between zeolite, sodium carbonate and sodium bicarbonate is between 1: 0.3 and 1.6: 0.2 - 2.0 based on water free bass; wherein in the case of the spray-dried granules containing zeolite and sodium carbonate, these are mixed with 0.1 to 3 parts by weight of particulate hydrated sodium silicate, calculated on an anhydrous basis, with a Na 2 O: SiO 2 molar ratio in the range 1: 1.5 to 1 : 2.5 before absorbing 0.2 to 1.6 parts of said nonionic detergent on the 2eolite carbonate bicarbonate grains or before absorbing 0.2 to 1.5 parts of said nonionic detergent on the zeolite carbonate silicate grains. % 7810357-1 A phosphate-free detergent according to claim 1, characterized in that it comprises grains of ion-exchanging zeolite, sodium carbonate, sodium bicarbonate and nonionic detergent in which the proportions of said components are in the range 1: 0.3 - 1.6: 0, 2 - 1, 5: 0.4 - 1.7. A detergent according to claim 1, characterized in that the ratio of bicarbonate to carbonate is in the range 1: 2 to 2: 1, said zeolite being a type A zeolite with crystalline, amorphous or mixed crystalline and amorphous structure and the The nonionic detergent is a higher-fat alcohol-polyethylene oxide condensate in which the higher-fat alcohol has 10 to 18 carbon atoms and the polyethylene oxide has 3 to 30 moles of ethylene oxide per mole of higher-fat alcohol, wherein the proportions of zeolite, carbonate, bicarbonate, water and nonionic detergent is in the range of 15 - 40%, 10 - 25%, 8 - 22%, 2 - 10% and 15 - 25% respectively. A detergent according to claim 2, characterized in that it has a bulk density in the range 0.65 - 0.85 g / ml, has a granular shape with particle sizes in the range 0.095 - 3.36 mm (6 - 160 mesh) , said spray-dried granules further containing sodium silicate having a Na O: SiO 2 molar ratio in the range 1: 1.6 to 2 2 l: 3.2, the zeolite having the formula (Na 2 O) 6 - (Al 2 O 3) 6 - (sio 2 ) 12_24. 20-27 H 2 O and the proportion of sodium silicate in the detergent is 3 - 20% by weight. A phosphate-free detergent according to claim 1, characterized in that it comprises said mixture of spray-dried granules containing ion-exchanging zeolite and sodium carbonate and aqueous sodium silicate powder, in which the proportions of said components are in the range 1: 0, 1 - 1: 4: 0, 1 - 0.6 and that 0.2 to 1.0 parts of nonionic detergent is absorbed in said mixture. A detergent according to claim 5, characterized in that said zeolite is a type A zeolite with crystalline, amorphous or mixed crystalline and amorphous structure and that the detergent is a higher-fat alcohol-polyethylene oxide condensate in which the higher-fat alcohol has 10 to 18 carbon atoms and the polyethylene oxide has 3 to 30 moles of ethylene oxide per mole of higher fat alcohol, the ratio of zeolite to carbonate being in the range of 1: 0.2 to 1.0 on the anhydrous basis and the weight percentages of zeolite, carbonate, silicate, nonionic detergent and water included are in the ranges 25 - 70%, 8 - 35%, 5 - 15%, 15 - 25% and 2 - 15% respectively. A detergent according to claim 6, characterized in that it has a bulk density in the range of 0.65 - 0.85 g / ml, has a granular shape with particle sizes in the range of 0.095 - 3.36 mm (6 - 160 mesh), wherein said aqueous sodium silicate particles have a particle size in the range of 0.74 - 0.149 mm (100 - 200 mesh) and adhere to the other constituents therein, said zeolite having the formula and the nonionic detergent being a condensation product of a higher fat alcohol having 12 - 18 carbon atoms and 5 - 12 moles of ethylene oxide per mole of fatty alcohol. A method of preparing the detergent composition according to claim 1, characterized in that it comprises spray drying a mixture of said zeolite, water and sodium carbonate or sodium carbonate and sodium bicarbonate to a moisture content in the range 2 - 15%, mixing said granules with aqueous sodium silicate in particulate form; and with said granules or with a mixture of said granules and aqueous sodium silicate, said liquid nonionic detergent mixes so that the detergent is absorbed in the granules. A method according to claim 8, characterized in that it comprises spray drying an aqueous mixture of said zeolite, sodium carbonate, sodium bicarbonate and water, which mixture is spray dried to a water content in the range of about 2-12% so that the proportions of zeolite, sodium carbonate and sodium bicarbonate in the spray-dried granules produced are in the range 1: 0.3 - 1.6, 0.2: 1.5, calculated on an anhydrous basis, after which said granules are mixed with 0.4 - 1.7 parts of nonionic detergent in liquid form . A method according to claim 9, said ion exchange zeolite is a synthetic sodium characterized in that aluminum silicate, that the nonionic detergent is a higher-fat alcohol-polyethylene oxide condensate, in which the higher-fat alcohol has 10-18 carbon atoms and the polyethylene oxide has 3 - 30 moles of ethylene oxide per mole of higher-fat alcohol, that the aqueous mixture which is spray-dried comprises 10 - 35% synthetic zeolite, 5 - 20% sodium carbonate, 10 - 30% sodium bicarbonate and 25 - 60% water, and that the proportions between bicarbonate and carbonate is in the range 1: 1 to 4: 1 in the aqueous mixture and in the range 1: 2 to 2: 1 in the spray dried grains. 7810337-1 58 11. ll. A method according to claim 10, characterized in that the product has a bulk density in the range 0.65 - 0.85 g / ml, that the aqueous mixture which is spray-dried further comprises 2 - 15% by weight of water-soluble sodium silicate with a Na 2 O: SiO 2 molar ratio in the range 1: 2 to 1: 3 so that the spray-dried product contains between 3 and 20% thereof, that the zeolite is of type A with crystalline, amorphous or mixed crystalline and amorphous structure and that the nonionic detergent is a condensation product of a higher-fat alcohol with 12. - 15 carbon atoms and 5 - 12 moles of ethylene oxide per mole of fatty alcohol, and that said aqueous mixture of zeolite, carbonate, bicarbonate, silicate and water is a "crutcher" mixture made by making a slurry of water, sodium carbonate and sodium bicarbonate , and mixing it with sodium silicate until a gel is obtained, after which the gel is subjected to shear to reduce its viscosity, followed by further addition of silicate until the desired content is reached, after which the mixture is atomized by spraying it from a circular nozzle having an inner diameter in the range 0.5 - 2.0 mm at a pressure of 10 - 50 kp / cm 2, after which the spray-dried product is sieved to sizes in the range 0.095 - 3.36 mm (6 - 160 mesh), after which the nonionic detergent The spray-dried particles are applied to the spray-dried particles as they are tumbled in a tumbling cylinder, by spraying the detergent in a liquid state, at a temperature in the range of 20 - 70 ° C, on the moving surfaces of the spray the particles to form particles with sizes in the range 0.095 - 3.36 mm (6 - 160 mesh).