NL8200804A - BASIC GRANULES FOR THE PREPARATION OF DETERGENT MIXTURES. - Google Patents

Description

Λ 4.

VO 3121

Basic granules for the preparation of detergent mixtures.

The invention relates to basic granules suitable for the preparation of builder-provided nonionic detergent mixtures. More particularly, it relates to such granules which are substantially inorganic in nature and include sodium carbonate, sodium bicarbonate, zeolite, sodium silicate and bentonite and / or polyacrylate, and which can absorb nonionic detergent in liquid form to obtain free-flowing, particulate builder-supplied nonionic detergent mixtures. The invention also relates to the preparation processes, the prepared mixer suspensions and detergent mixtures, which mixtures have improved washing properties, although they may deposit less residue on washed materials despite the presence of zeolite and silicate.

Synthetic organic detergent compositions containing water softening aluminum silicates, such as zeolites, have been invented and marketed in recent years. In such mixtures, which also contain a synthetic organic detergent or surfactant, the zeolite acts as a calcium sequestrant and as a builder for the organic detergent, improving its cleaning performance, especially in hard water. In such blends, sodium silicate has also been used as a builder and as a corrosion preventive additive for protecting aluminum parts of the washing equipment with which the aqueous solutions of the detergent mixture come into contact during washing. The silicates may also be suitable to counteract negative effects that magnesium ions in the wash water could have on the washing activity of the detergent mixture. It is further contemplated that the silicate promotes the formation of more stable detergent granules, especially when they are manufactured by spray drying a mixture of detergent mixture components from the soap mixer. However, it is recognized that zeol-30s often tend to deposit as a noticeable residue on the wax washed in aqueous cleaning media containing them and several investigators have reported that the presence of a silicate in such medium with zeolite increases the amount of residue deposited.

Bentonite, a swelling clay, with relatively minor hardness ion exchange capacity, has been suggested for use in various detergent products, such as soap bars and laundry detergents, in which it has often served primarily as a filler. However, in certain cases it seems to perform other functions. For example, e.g. 10 in U.S. Patent 1,166,039 discloses that it promotes the preparation of homogeneous detergent suspensions when such suspensions contain phosphate or phosphates, respectively. contain. Normally, however, addition of clays to detergent mixtures is avoided because they are insoluble and they could deposit on the materials to be washed. Indeed, clay soil removal is one of the test methods used to determine detergent efficiency. Despite the fact that the addition of bentonite could be expected to exacerbate the residual problems of washing laundry with aqueous media containing detergent mixtures containing zeolite and silicate, it has surprisingly been found that the deposition of residue is reduced.

Also, the ability to bind calcium ion increases.

Polyacrylates, often of relatively high molecular weight, have been proposed as detergent mixture components. They have been disclosed as components of powdered and suspended detergents and have been suggested as a substitute for phosphate builders in non-phosphate detergents. The polyacrylates are known to have dispersant properties and a producer of these materials has suggested using them for dispersant applications such as maintaining the suspension of pigments in paints. Furthermore, it is known that in certain aqueous media they tend to inhibit the deposition of insoluble calcium compounds and the redeposition of insoluble materials on washed laundry. Although polyacrylates have been included in detergent formulations, it is believed that the present soap mixer blends, base grains, and detergent blends are new and not obvious to the 8200804. The presence of a very small amount of a special type of polyacrylate in the described reds in conjunction with the other components of such recipes has been found to result in an improved product with better cleaning properties, which can be prepared using practicable preparation measures.

According to the invention, free-flowing base grains, on which nonionic detergents may be absorbed to form particulate builder containing synthetic nonionic organic detergent products with improved washing properties, which, after rinsing, leave small amounts of deposits on fabrics washed with such products. , by weight of about 15 - 30 $ sodium carbonate, 10 - 22.% sodium bicarbonate, 10 - 50 $ a bit more soft end aluminum silicate, 0 - 18% sodium silate and 1 - 20 $ bentonite and / or 0.05 -15 2 $ polyacrylate with a molecular weight in the range 1000-5000.

Such products will normally contain from 1 to 15% moisture and can be formed into organic detergent mixtures by adding liquid nonionic detergent thereto so that the detergent is absorbed and the product obtained is still free flowing. The amount of detergent used will normally be such that the finished detergent mixture contains about 8-30% by weight thereof.

The presence of the polyacrylate promotes that the base grains are more absorbent to the liquid nonionic detergent. Task also improves spray drying operations with the result that less material adheres to the dryer walls thereby increasing throughput rates through the spray tower and reducing the number of shutdowns and cleanings that may be required.

The various components of the base grains of the invention, except for water, are normally in the solid state, although when added to the soap mixer, some may be in the form of hydrates or may be dissolved or dispersed in an aqueous medium, like water. The sodium bicarbonate is anhydrous, and sodium carbonate is commonly used as the soda ash. However, the carbonate hydrates, such as the monohydrate, may optionally be used, and in some cases it may be possible to use other carbonates, 8200804-bis bicarbonates, such as other alkali metal salts, e.g. the potassium salts to replace at least some of the sodium salt, although the sodium salts are very preferred. When silicate is present, it is usually added to the soap mixer as an aqueous solution, which normally has 1 + 0 - 50 # solids content, e.g. 1 + 7.5 #, and preferably, J is added at the end of the mixing process. The silicate used will usually have a Na 2 O / SiO 2 ratio in the range of 1: 1.1+ to 1: 3, "preferably 1: 1.6 to 1: 2.1+ or 1: 1.6 and most preferably 1: 2 to 1: 2.1+. Although 10 sodium silicate is the preferred silicate, part of the sodium silicate be replaced with potassium silicate or another suitable soluble alkali metal silicate salt.

The zeolites employed include crystalline, amorphous and mixed crystalline amorphous zeolites of both natural and synthetic origin which are satisfactory in satisfactory activity to counteract calcium hardness ions in wash waters. Preferably, such materials are able to react sufficiently quickly with the calcium ions that they alone or together with other water softening compounds in the detergent soften the wash water before negative reactions of such ions with other components of the synthetic organic detergent mixture. takes place. The zeolites used can be characterized as having a high exchange capacity for calcium ion, which is normally from about 200 -1 + 00 or more mgeq. calcium carbonate hardness per g aluminum silicate, 25 ", preferably 250-350 mgeq / g. Also, they preferably have a hardness depletion rate of residual hardness of 0.02-0.05 mg calcium.

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carbonate / dm per minute, preferably 0.02 - 0.03 mg / dm and less than 3 0.01 mg / dm in 10 minutes, all on an anhydrous zeolite basis.

Although other ion exchange zeolites can be used, normally the particulate synthetic zeolite builder particles used in the practice of the invention will be of the formula

(Jia2 °) x. (Al2 O3) y. (SiO2), e.g. HgO

wherein x is 1, y is 0.8 - 1.2, preferably about 1. z is 1.5 - 3.5, preferably 2 - 3 or about 2, and w is 0 - 9, preferably 2 , 5 - 6.

8200804 - 5 -

The zeolite should be a monovalent cation-exchanging zeolite, ie it should be an aluminosilicate of a monovalent cation such as sodium, potassium, lithium (when "usable") or other alkali metal, ammonium or hydrogen (sometimes). The cation of the zeolite used is an alkali metal cation, in particular sodium or potassium and most preferably sodium.

Crystalline types of zeolites useful as good exchangers 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, X and Y are preferred. Mixtures of such molecular sieve zeolites can also be used, especially when zeolite type A is present. These crystalline types of zeolites are known and are further described in Zeolite Molecular Sieves,

Donald W. Breek, (19? M, John Wiley & Sons. Typical commercially available zeolites of the above structure types are listed in Tables 9 * 6 on pages 7-9 of the above work. Such Zeolites Are Known Some and other such suitable zeolites have been described in many patents in recent years for their use as detergent mixture builders.

The zeolite used in the invention is usually synthetic and is often characterized by having a network of pores of substantially uniform size in the range of about 3-10 2, often about U'2 (normal), which size alone is affected by the unitary structure of the zeolite crystal. Preferably it is of type A or similar structure, particularly described on page 133 of the above work. Good results have been obtained when using a molecular kA molecular sieve zeolite in which the monovalent cation of the zeolite is sodium and the pore size of the zeolite is about 1 + 2. Such zeolite molecular sieves are described in U.S. Patent 2,882.2 ^ 3, in which the zeolite A is mentioned.

Molecular sieve zeolites can be prepared in either a dehydrated or calcined form containing about 0 or about 1.5 to about 3% moisture or in hydrated or water-loaded form containing additional bound water in an amount of about b to 8200804 About 6% of the total weight of the zeolite, depending on the type of zeolite used. The hydrated form of the molecular sieve zeolite (preferably about 15-70% hydrated) is preferred when carrying out the invention. if such a crystalline product is used. The preparation of such crystals is known. For example, e.g. in the preparation of zeolite A, as mentioned above, the hydrated zeolite crystals formed in the crystallization medium (such as aqueous amorphous sodium aluminosilicate gel) used without the high temperature dehydration.

IQ (calcination to 3% or less water content) normally used in preparing such crystals for use as a catalyst, e.g. cracking catalysts. The crystalline zeolite, in either fully hydrated or partially hydrated form, can be recovered by filtering the crystals of the crystallization medium 15 and drying it in air at ambient temperature so that their water contents are in the range of about 5-30%, preferably about 10-25 $ such as 17-22 $. However, the moisture content of the molecular sieve zeolite used may be much lower as previously described, in which case the zeolite will usually be hydrated during mixing and other operations.

Preferably, the zeolite should be in a finely divided form with a particle diameter up to 20 microns, e.g. 0.005 or 0.01 - 20 microns, preferably 0.01 - 15 microns, and most preferably 0.01 - 8 microns average particle size, e.g. 3 - 7 or 12 microns, if crystalline and 0.01 - 0.1 microns, e.g. 0.01 - 0.05 micron if amorphous. Although the final particle sizes are much smaller, the zeolite particles will usually have sizes in the range of 100 - 00 mesh, preferably 1 - 0 - 325 mesh. Smaller zeolites will often become a nuisance rebar and those of larger particle sizes will not adequately and satisfactorily cover the carbonate-bicarbonate base particle cores to which they are deposited during the spray drying or mixing in the soap mixer to form the base beads.

The bentonite used is a colloidal clay (aluminum silicate) containing montmorillonite. Montmorillonite is a hydrated 8200804-7 aluminum silicate in which about 1/6 of the aluminum atoms may have been replaced by magnesium atoms and loosely combined with varying amounts of hydrogen, sodium, potassium, calcium, magnesium and other metals. The type of bentonite clay specifically described herein for preparing the invented base granules is known as sodium bentonite (or Wyoming or western bentonite), which is normally a light to cream-colored insensitive powder which is a colloidal suspension with strong thixotropic properties in water. forms. In water, the swelling capacity of the clay will usually. in the range of 3-15 cm / g,

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10 preferably 7-15 cm / g and its viscosity at a 6% concentration in water will usually be in the range of 3-30 cps, preferably 8-30 cps. Preferred swelling bentonites of this type are those sold under the trade name THIX0-JEL, as industrial bentonites by Benton Clay Company, a sister organization of Georgia Kaolin Co. Such materials are selectively mined and enriched bentonites, those considered most suitable and those identified as THIXO-JEL's Hos. 1, 2, 3 and 1..

Such materials are with a pH ($ 6 concentration in water) in the range of 8-9.1, maximum free moisture contents of about $ 8-20 and specific gravities of about 2.6 with the powdered type being about $ 85 a. 200 mesh US Sieve Series strainer passes. Such materials show an interchangeable calcium oxide percentage in the range of about 1 - 1.8, and with respect to magnesium oxide such percentage is normally in the range of 0.01 - 0.11. Typical chemical analyzes of such materials are from 61.8 - 73.0 $ SiO 2, 1.1 - 1.8 $ Al2 O3, 1.6 - 2.7 $ MgO, 1.3 - 3.1 $ CaO , 2.3-3.1 $

FegO 2, 0.8 - 2.8 $ Ha 2 O, and 0.1 - 7.0 $ KgO. Although such bentonites are preferred, equivalent materials from other sources can replace them.

30 'The polyacrylate present in the preferred base beads of the invention is a low molecular weight polyacrylate, the molecular weight usually being in the range of from about 1000 to 5000, preferably 1000 to 3000, and most preferably 1000 to 2000, or about 2000 The polyacrylate can be partially or completely neutralized eg about 1/2 or 1/3 sodium salt. Although modified polyacrylics may be substituted for the "described sodium polyacrylate theirs, including some other alkali metal polyacrylates and hydroxylated polyacrylates, it is preferred that such replacement be limited to a minor content of the material and preferably the polyacrylate be an unsubstituted sodium polyacrylate Such materials may be purchased from the Alco Chemical Corporation under the name Alcosperse The sodium polyacrylates are available as clear amber liquids or powders, the solutions of which ring about 25 - b% solids content ), for example, 30%, and with a pH of such a solution or of a 30% aqueous solution of the powder in the range of about 7.5 to 9.5, preferably about 9. Such materials are completely soluble in water and they have been used as dispersants They have been found to have the ability to calc ions and have been used to prevent deposits of insoluble calcium compounds from aqueous solutions.

The presence of the polyacrylate, even in a very small amount, promotes mixing of the various mixing components in the soap mixer including in preferred recipes of ultramarine-20 blue, which, when poorly distributed, can color laundry washed with detergent made from the base grains. The polyacrylate also promotes an even distribution of fluorescent brighteners in the soap mixer and detergent mixture thereby promoting even wax clarity. Furthermore, the polyacrylate 25 makes the total end product (with the exception of the non-ionic detergent content) more homogeneous. Processing aids that may be present for it. prevention of gelation, and deposition of inorganic materials in the soap mixer during mixing, and standing thereof, are more evenly dispersed in the soap mixer mixture with increasing processing efficiency. The polyacrylate promotes that the base granules obtained by spray drying are more absorbent to the liquid nonionic detergent sprayed on the granules. In some cases, it increases the detergent containment ability of the granules while they are still free-flowing. Spray drying operations are improved because less 8200804 ♦ * - 9 - of the sprayed material adheres to the dryer walls, increasing throughput through the rigging tower and reducing the number of shutdowns and cleanings.

The only other material necessary for preparing the present granules is water and during the drying of the granules their moisture content may decrease so that the product is substantially anhydrous. Although it is preferable to use deionized water so that its hardness ion content can be very low and so that metal ions that promote decomposition of some organic materials which may be present in the final cores and detergent are minimized --------, normally city or tap water can be used instead. Normally, the hardness content of such water will be less than 150 ppm, like CrCQ, more preferably the hardness content will be less. than 100 ppm and most preferably it will be less than 50 ppm.

15 Although fairly concentrated aqueous soap mixtures of silicate, carbonate, bycarbonate, zeolite and bentonite and / or polyacrylate may "freeze" in the soap mixer due to interactions of its components if maintained for longer than a permissible time, processing aids present in the soap mixer when silicate is present, and consequently in the finished base granules and detergent mixture, to prevent premature solidification or gelling of the mixture. Preferably, this citric acid and magnesium sulfate. Instead of citric acid, soluble citrates such as sodium citrate, and although it is preferred to use anhydrous magnesium sulfate, various hydrates thereof, such as epsomr salts, may also be used, and magnesium citrate may be substituted for them.Instead of the preferred anti-gelling system, other agents and suitable systems for maintaining the soap liquid are substituted, such as sodium 30 sesquicarbonate, used to replace some of the sodium carbonate and sodium bicarbonate.

Various additives such as fragrances, enzymes, colorants, bleaches and flow promoters can often be sprayed on or otherwise mixed with the base granules after their preparation with the nonionic detergent or separated therefrom. 10 so that they are not adversely affected by the spray drying operation and also so that their presence in the spray dried granules prevents the absorption of nonionic detergent. However, for stable and normally solid additives, mixing with the inorganic salt suspension in the mixer is also feasible. For example, it is contemplated that colorants and fluorescent brighteners are normally present in the soap mixer mixture from which the subject base grains are atomized. The preferred colorant is ultramarine blue, but other stable pigments and dyes can be used together or instead. Among the fluorescent brighteners, Tinopal 5BM is most preferred. However, various other cotton brighteners, such as those sometimes referred to as CC / BAS brighteners, derived from the reaction product of cyanuric chloride and a disodium salt of diaminostilbene disulfonic acid, may also be used, including variations thereof with respect to substituents on the triazine and aromatic rings . This class of brighteners is known in the detergent field and will very often be used if no bleach components are present in the final product. In those cases, bleach-stable brighteners can be used. Listed below are the benzidine sulfone disulfonic acids, naphthotriazolylstilbene sulfonic acids and benzimidazolyl derivatives. Polyamide brighteners, which may also be present, include amino coumarin or diphenylpyrazoline derivatives, and polyester brighteners that may also be used include naphthotriazolyl stilbenes. All such brighteners are normally used as their soluble salts, but they can also be used as the corresponding acids. The cotton brighteners will usually contain predominant amounts of the brightening system.

Of the materials which can subsequently be added to the spray dried base grains, the most important of course is the nonionic detergent. Although various nonionic detergents with satisfactory physical properties can be used, including condensation products of ethylene oxide and propylene oxide with each other and with hydroxyl-containing bases, such as nonylphenol or 8200804-11 oxo-type alcohols, it is usually recommended that the nonionic detergent is a condensation product of ethylene oxide and a higher fatty alcohol. In such products, the higher fatty alcohol contains 10-20 carbon atoms, preferably 12-16 carbon atoms and the nonionic detergent contains about 3-20 ethylene oxide groups per mole, preferably 6-12. Such detergents are manufactured by Shell Chemical Company and are sold under the trade names Neodol 23-6-5 and 23-7-

The enzyme preparations, which are normally added afterwards to the base granules, may be of any of a variety of commercially available product including Alcalase, prepared by Novo Industri, A / S and Maxatase, both of which are alkaline proteases (subtilisin). Although the alkaline proteases are preferred, amylolytic enzymes such as amylase as well as proteolytic enzymes can be used. The listed mixtures usually contain active enzymes in combination with an inert powdery carrier such as sodium or calcium sulfate, and the amount of active enzyme can vary widely usually from 2 - 80% of the commercial formulation. The fragrances used, which are usually heat sensitive, and may contain some volatile solvent material, such as alcohol, are normally synthetic fragrance materials, sometimes mixed with natural components, and generally include alcohols, aldehydes, terpenes, fixatives and other normal fragrance components. The flow promoters, such as special clays, which are sometimes added to detergent products, or often suitable for improving flowability and reducing tackiness of various blends, are not necessary in the present cases, presumably partly due to the presence of the bentonite and / or the polyacrylate.

However, they can optionally be added to further improve flowability.

The amounts of the various components in the base grains will be such as to result in free-flowing of the grains and they are sufficiently absorbent for a non-ionic detergent applied thereto in a liquid state, so that the detergent mixture which is added by adding such detergent is prepared, also 8200804-12 - is satisfactorily free-flowing. Also, of course, the detergent mixture prepared from the base grains must be an effective detergent in which the builders present support the organic detergent in aqueous solutions of the mixture and it is important that the product obtained is one that does not adversely affect zeolite. particles (possibly with other materials, such as normally water-soluble silicates) on washed materials. It has been found that fairly satisfactory base grains for this purpose, when silicate is present, may contain by weight 15 - 30 # sodium carbonate, 10 - 22% sodium 10 µm bicarbonate, 20 - 0% water softening aluminum silicate (zeolite), 3 or ^ - 12 # sodium silicate and 1 - 15 # bentonite as the active components, and 1 - 15 # water. In such granules, the aluminum silicate will preferably be a sodium zeolite containing 15-25% by weight of hydration water, and more preferably such zeolite will be zeolite A. The preferred weight ratio of sodium carbonate: sodium bicarbonate in the product is in the range of about 1-3, the prepared

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granules have a bulk density in the range of 0.6 - 0.9 g / cm,

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more preferably 0.7 - 0.8 g / cm and the grain sizes are in the Hos range. 10-100 UVS. -Sieve-Series, prefer 10 - βθ Ü.S. Sieve Series ..

20 Further preferred amounts of the components are 20 - 25 # sodium carbonate, 13 - 19 # sodium bicarbonate, 30 - 37 # hydrated zeolite, 5 - 8 or 10 # sodium silicate, 5-8 # bentonite and h - 10 # water, excluding the hydration water of the zeolite. In such preferred products, the weight ratio of sodium 25 carbonate to sodium bicarbonate is in the range of 1-2.

If a polyacrylate is present along with the zeolite in the base grain mixture, the amount thereof will normally be in the range of 0.1 - 2 #, preferably 0.2 - 1.6 #, and more preferably 0.8 -1, J + # . Amounts of additives and processing aids and fillers, if present in the base granules, will normally be limited to 20 # thereof, preferably 1 - 10 # and more preferably 3 - 7 # thereof. The amounts of the processing aids when magnesium sulfate and citric acid are used will normally be from 1-3 # magnesium sulfate, more preferably 1.5-2.5 thereof, and 0.2-1 # sodium citrate, more preferably 0.2-0.5 thereof. With regard to pigmentation and fluorescent brightening - the agents will be the preferred amounts of 0.05 - 0.6 $ pigment, such as ultramarine blue, more preferably 0.2 - 0.4 $ and 0.1 - 4 $ fluorescent brightening agent, more preferably 1 or 1.5-3% thereof. Such amounts of processing aids and additives apply to different types of granules according to the invention when such auxiliary substances or additives are used.

The amounts of the various components in the soap mixer mixture and in the base granules when preparing the granules include polyacrylate but omitting bentonite will be such that the mixture is uniform or substantially uniform, and the granules are free-flowing and sufficiently absorbent for a non-ionic detergent to be applied to it in a liquid state, so that the detergent mixture prepared therefrom by the addition of such a detergent is also satisfactorily free-flowing. Satisfactory base grains for accomplishing this purpose have been found to include by weight 15 - 30% sodium carbonate, 10 - 22% sodium bicarbonate, 20 - 40% water softening aluminum silicate (zeolite), 3 or 4 - ± 3% sodium silicate, and 1 - 2% polyacylate, as the active components and 1 - 12 or 15 $ water. The preferred weight ratio of sodium carbonate / sodium bicarbonate in the product is in the range of about 1-3, with the prepared granules having a bulk density in the range of 0.5-0.8 g / cm 2, preferably 0.7-0 .8 g / cm, and the grain sizes are in the range of Ho.-10 - 100 US -Sieve -Series, prefer 10 - 60 U.S. Sieve Series. Further preferred how-25 quantities of components are 20 - 25 $ sodium carbonate, 13 - 19 $ sodium bicarbonate, 30 - 37 $ hydrated zeolite, 7 - 15 $ sodium silicate, 0.5 - 1.5 $ sodium polyaczylate and 3 - 10 $ water, with the exception of the hydration vessel of the zeolite. In more preferred products of this type, the weight ratio of sodium carbonate to sodium bicarbonate is in the range of 1-2.

When the granules to be prepared have little or no water-soluble silicate as previously indicated with respect to other types of the invented granules, the amounts of the different components in the base granules will be such that free flowing is obtained and sufficient absorbency for 8200804 - Ik - a nonionic liquid detergent in its condition is applied thereto so that the detergent mixture resulting therefrom is prepared by addition of such detergent still satisfactorily free-flowing.

It is also important that the product obtained is such that no dangerous deposition of zeolite particles (possibly with other substances) on fibrous materials is obtained. It is also a concern for the basic granules to be prepared that they have a suitable bulk density and color. It has been found that such base grains satisfactorily per pulp contain for this purpose 15-30 $ sodium carbonate, 10-22 $ sodium ^ 10 bicarbonate, 10-15 $ water-softening aluminum silicate (zeolite), 0-3 $ sodium silicate and 3-20 $ bentonite as the active components and 1 - 15 $ more. The reported percent water is more water and does not include the hydration water of the zeolite. Accordingly, the percentage of zeolite includes the hydration water. In some cases, the product may be vessel-free with respect to free moisture content, but such cases are rare, and it is normally inconvenient that at least a small amount of more water is present in the base grains to prevent unwanted pulverization thereof, which sometimes occurs with special water. free recipes. The preferred weight ratio of sodium carbonate / sodium bicarbonate in the product is in the range of about 1 to about 3, the granules prepared have a bulk density in

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the range of 0.6 - 0.9 g / cm, more preferably 0.6 or 0.7 - 0.8 g / cm and the grain size dimensions are in the range of Nos. 10 - 100 USSieve Series, more preferably 10 - 60 US Sieve Series-. Further preferred quantities of components are 20 - 27 $ sodium carbonate, 14 - 21 $ sodium bicarbonate, 20 - 50 $ hydrated zeolite, 0 $ sodium silicate, 5 - 20 $ bentonite and 1 - 5 $ water, excluding the hydration water of the zeolite. In such more preferred products, the weight ratio of sodium carbonate / sodium bicarbonate is in the range of 1-2. When silicate is present in such base grains, it will be advisable to limit its content to $ 2, more preferably to $ 0.5-1 $. Other preferred amounts of major components of the invention are 35-15 $ hydrated zeolite and 5-15 $, more preferably 10-15 $ bentonite.

As a polyacrylate in such. base grain mixture if 8200804-15, the amount will normally be in the range of 0.05-0.5, preferably 0.05-0.3, more preferably 0.1-0.2%. Amounts of additives and processing aids and fillers when present in such hash granules will normally be limited to 20% 5 thereof, preferably 1 - 10% and more preferably 3-7% thereof, and the amounts thereof will be as previously stated.

Although it has been found that detergent mixtures prepared from the base grains present do not require the presence of any anti-corrosion additive to replace the silicate, it is within the invention to use such suitable materials and it is recommended to use such that are stable under mixing and spray drying and do not adversely affect such operations. Such aati corrosion additives or antioxidants can be organic or inorganic with inorganic materials normally being preferred and they will preferably be chosen for suitability for preventing corrosion of aluminum parts from washing machines. If it is desired to continue to use a silicate for such a purpose or to use a silicate for its magnesium hardness treatment effect, a powdered silicate n®r-2Q will be more preferably preferred, such as aqueous sodium silicate, which is commercially available under the name Britesil, produced by Philadelphia Quartz Co. (ïïa ^ O: SiO ^ = 1: 2sk), and this will be added afterwards. However, other normally solid soluble silicates, preferably of alkali metals, may also be added afterwards to the granules of the invention in which nonionic detergent has been pre-absorbed. If the manufactured product is desired to have fabric softening properties, softening materials, preferably in dry powder form, may also be suitably added to the base grains afterwards. This class of materials is known and the most common of such softeners are cationic compounds, especially quaternary ammonium compounds, such as quaternary ammonium halides. Especially preferred are the higher alkyl, alkyl aryl and arylalkyl lower alkyl quaternary ammonium chlorides and bromides, such as distearylpyridylammonium chloride. From technical emollient materials, that is sold 8200804-16 - under the trade name Arosurf TA-100, produced by Bherex Chemical Company Inc. most preferred. Such compounds also have anti-static and antibacterial properties, but if desired other antibacterial additives can also be used, preferably also incorporated in the product by post-addition.

It is an important feature of the present invention that an effective builder-containing detergent mixture based on nonionic detergent alone can be prepared by a technically feasible process, but sometimes it may be desirable that an anionic surfactant or detergent component is also present in the finished product ,. usually as a contribution to foaming properties and additional cleaning effects. Normally, it is not recommended to add such anionic detergent materials into the soap mixer, so that if used, it is recommended to add them afterwards to the spray dried base granules and normally this will be after addition after absorption by the granules of the liquid non-ionic detergent. Although various types of anionic detergents, preferably entirely in powder form, and / or sometimes mixed with builder materials, may be used, the preferred linear alkylbenzene higher sulfonates, higher fatty alcohol sulfates and polyoxyethylated higher fatty alcohol sulfates. In such products, the higher alkyl and higher alcohol parts will normally have 8 "- 20, preferably 12 - 16 carbon atoms and the detergents will be present as their water-soluble alkali metal salts, preferably as sodium salts. The ethoxylated alcohol sulfate will normally contain 3-20 moles of ethylene oxide per mole of fatty alcohol.

The ranges of the amounts of the different granular components in the finished detergent mixture can be easily calculated from those given for the base granules, less the amounts of detergent and other materials added to the granules afterwards. Therefore, if the finished detergent mixture contains only nonionic detergent added thereto, so that the final product contains 20% nonionic detergent, of the various ranges given for components in the base grains ranges of amounts 8200804 - IT - thereof can be calculated by multiplying with 0.8 barrel is (100 - 20) / 100. Likewise, when the amount of nonionic detergent (in compositions in which it is the only additive to the granules) can range from 8 - 25 # of the detergent mixture, the multiplication The tower will be 0.75 - 0.92 Usually the final percent nonionic detergent in the product will be in the 8 - 25% range, preferably from 15 - 22 # and more, most preferably about 20 #, but in some cases, for certain types of products, amounts will be preferred in the range of 8 - 13 # Normally, the percentage of fragrance in the final product will be in the range of 0.1 - 1 #, preferably of 0.2. 0, U # lie and h The percentage of enzyme will be from 0.5 - 3 #, preferably 1 or 1.5 - 2.5 # and the percentage of flow improver that can be added afterwards will be less than 2 #, preferably less than 1 # . Of course, in calculating the ranges of the granule components in the final blend, except that these calculations are based on the percentage of nonionic detergent in the final product (added afterwards), the percentages of other post-added additives will also need to be considered. Also, if any post-additions are made using aqueous solutions of the additives, it will also affect the moisture content which will usually be maintained in a up to 12 # area but can sometimes be increased to 15 #.

When polyacrylate is used and bentonite is omitted, the ranges of the amounts of the various detergent mixture components are 13 - 28 # sodium carbonate, 8 - 18 # sodium bicarbonate, 15 - 35 # water softening aluminum silicate, 3 - 10% sodium silicate, 0 , 1 - 1.6 # polyacrylate, 8 - 30 # nonionic detergent and 1 -10 # water. Preferably such areas are 16 - 21 # sodium carbonate, 10 - 15 # sodium bicarbonate, 22 - 32 # hydrated zeolite, 8 -30 13 # sodium silicate, 0.5 - 1.5 # sodium polyacrylate, 3-6 # (and sometimes 3 - 10 #) moisture and 10 - 22 or 25 # non-ionic detergent. The processing aids, brightness enhancers and dye percentages in the finished detergent mixture will be about the same as in the base granules, preferably in the range 0.2 - 0.6 # 35 for sodium silicate (due to the addition of citric acid) and 8200804 - 18 - 1-2 $ for the magnesium sulfate, 0.1 - 0.3 $ for the ultramarine blue and 1.5 - 2 $ for the fluorescent brightener. The enzyme content will be in the 0.5 - 3 $ range, usually 1 - 2 $ and the fragrance content will be 0.1 - 1 $, preferably 0.2 - 0.0 H $.

The ranges of the amounts of the different grain components in the spray-dried portion of the final detergent mixture, when little or no silicate is present, can be calculated in the manner previously described. With regard to components added afterwards, the percentages of non-ionic detergent will be the same as previously stated, the percent of perfume in the final product will be in the range of 0.1 - 1, preferably 0.2 - 0. $, The percentage of enzyme will be from 0.5 - 3 $, preferably 1-2 $, and if a hydrated silicate is added afterwards, the amount thereof will normally be from 2 - 10 $, preferably 3 - 8 $ , e.g. about 15 $ 5. If a softening compound is present in the final product, the amount thereof will normally be in the range of 3-12, preferably 5-10 $ and when anionic detergent (s) is or are used, the amount thereof will be limited to no more than that of the nonionic detergent and the total weight of anionic and nonionic detergents in the final product will be within the ranges previously given for the nonionic detergent alone. If anionic detergent is used, the amount thereof will normally range from 0.2 to 0.8 times the weight of the nonionic detergent. Of course, in calculating the ranges of grain components in the final blend, except that such calculations are based on the percentage of nonionic detergent in the final product (added afterwards), percentages of other additives added afterwards should also be considered. Even if some additives added afterwards are made with the aid of their aqueous solutions, this will also affect the moisture content, but will usually be kept in the 1-12 $ range for the final product, which can sometimes be increased to 15 $.

The base granules of the invention are spray dried from an aqueous soap mixture which normally contains about ho 35 to about 70 or 75 $ solids, preferably 50 - 85 $ with 8200804 - 19% residual water, preferably deionized water as previously described. , but city water can also be used. The soap mixer mixture composition ranges can be recalculated from the desired base grain composition areas based on the moisture contents of the beads and the mixture. Therefore, e.g. in a soap mixer mixture that must contain 50% moisture, from which mixture a base grain with 5% moisture content must be prepared (with neglect of the hydration water in the zeolite), the percentages of the components in the base grain should be multiplied by 10/19, which is is (100/2 ^ 100 - 5 J) · Above-10 calculations are satisfactory for components used at. does not decompose the spray drying operation but it is known that part of the bicarbonate is converted to carbonate upon drying at elevated temperatures in a spray tower. As a result, knowing the tower properties and drying conditions, so that the degree of bicarbonate decomposition is predictable, one can calculate the amount of carbonate and bicarbonate to be present in the soap mixture. When e.g. it is desirable to prepare a product containing about 22% sodium carbonate and about 16% sodium bicarbonate in those cases where about 1/3 of the bicarbonate decomposes to carbonate in the sputtering tower (causing two parts of carbonate to form three parts of decomposed bicarbonate) 2h% bicarbonate and 17% carbonate can be added to the soap mixer (on a dry basis).

With regard to the various recipes and calculations, it should be considered that the zeolite in the soap mixer mixture 25 and in the spray dried base granules and detergent mixture is hydrated to the extent of about 20% water of hydration but it is recognized that the degree of hydration may vary. However, for consistency and for the purpose of such calculations, such a constant degree of hydration should be assumed.

The soap mixer mixture from which the base granules of the invention are most preferably prepared by spray drying is one which is mainly inorganic and that content of organic material is usually limited to 10%, preferably to J% and most preferably h% on a dry matter basis. Among such organic materials that may be present are citric acid materials (citric acid and soluble citrates), 8200804-20 fluorescent brighteners, polyacrylate, dyes and pigments. Other organic materials may also be present, including hydrotropic salts, chelating agents and polyelectrolytes, but, as will be appreciated, the soap mixture will consist mainly of inorganic materials and water.

For the polyacrylate-containing granules, without bentonite, on a 100% solids basis, the soap mixture will normally consist of 10-25% sodium carbonate, 15-30% sodium bicarbonate with the sodium bicarbonate / sodium carbonate weight ratio in the range of 0.5 - 2, 20 - h0% water-softening aluminum silicate, U - 18% sodium silicate and 0.1 - 2% polyacrylate. If auxiliary auxiliaries are present, the amounts thereof will usually be on the same basis of 1-3% magnesium sulfate and 0 , 2 - 1% sodium nitrate. Preferably, in such soap mixer suspensions, the sodium polyacrylate content will be from 0.5-1.5%, and when processing aids and colorants are also present, the amounts thereof will be from 1.5-2.5% magnesium sulfate. 2 - 0.5% sodium citrate, 0.2 --0% + ultramarine blue and 1.5 - 3% fluorescent brightener, on a solid basis.

The soap mixer mixture is preferably prepared by successively adding various components thereof in a manner that will result in the best miscible, easily pumpable and non-settling spray-drying slurry. The order of addition of the different components can be varied depending on the circumstances, but it is highly desirable to add the silicate solution (if added) last, and if not last, at least add some gelation thereafter or hardening-preventing combinations of materials as processing aids. Normally, it is recommended that all or substantially all of the water to be added be added first to the soap mixer, preferably at about the processing temperature, after which the processing aids (if any) and other minor components, including pigments and fluorescent brighteners , and polyacrylates (if any) are added followed by the bentonite (if any), zeolite, bicarbonate, carbonate, and silicate (if any).

8200804 - 21 -

Usually, with such additives, each component will be thoroughly mixed before the next component is added, but the methods of addition may vary depending on the conditions so that additives are possible if practicable.

Sometimes, as with silicate, the components can be added in two or more parts. Different components can be pre-mixed before being added to speed up the mixing process. Normally, the mixing speed and power will be increased when the materials are added. E.g. low rates can be applied until after the addition of the last of the bentonite or zeolite, after which the rate can be increased to medium and then to high, before, during and after addition of all silicate solution.

The temperature of the aqueous medium in the soap mixer will usually be about room temperature or higher, usually in the range of 20 - 80 ° C, preferably 30 - T5 ° C, and most preferably kO-T0 ° C. Heating the soap mixture can promote dissolution of the water-soluble salts of the mixture and thereby increase miscibility, but the heating treatment, when performed in the soap mixer, can slow production rates and promote deposition of the mixture. Therefore, an advantage of having processing aids in the mixture is that they ensure that the desired non-gelling suspensions are obtained at both lower and higher temperatures. Temperatures higher than 80 ° C (and sometimes T0 ° C) will usually be avoided because of the possibility of decomposition of one or more soap mixture components, e.g. sodium bicarbonate. Also, in some cases, low soap mixer temperatures raise the upper limits of the soap mixer solids levels. probably as a result of the insolubility of normally gelling or depositing components.

Soap mixer mixing times for obtaining good suspensions can vary widely from 5 minutes for small soap mixers and for suspensions of higher moisture contents to k hours in some cases. The mixing times required to not bring all the soap mixer components essentially homo-35 together in a medium may be 10 minutes but may take up to 1 hour in some cases, although 30 minutes is a preferred upper limit. When discounting each initial mixing time, normal soap mixing periods will range from 15 minutes to 2 hours, e.g. 20 minutes to 1 hour, but the soap mixture should be such that it is mobile, not gelled or deposited, for at least 1 hour, preferably for 2 hours and more preferably k hours or more after completion of the preparation of the mixture and can even be mobile for 10 - 30 hours before being pumped out to the spray tower for situations where other preparation problems can be encountered.

The mixed suspension with the various salts and any other component thereof dissolved or in particulate form, evenly distributed therein, is transferred in a conventional manner into an atomization drying tower, which is normally placed at the soap mixer. The suspension is brought from the bottom of the soap mixer to a positive displacement pump, which presses it under high pressure through atomizing nozzles at the top of the usual atomizing tower (countercurrent or direct current), in which the droplets of the suspension pass through a hot drying gas, usually the combustion products of fuel oil or natural gas, in which the droplets are dried to the desired absorbent granular form. During drying, part of the bicarbonate (often 1 / k to 1/2, eg 1/3) can be converted to carbonate, with release of carbon dioxide, which, together with the content of polyacrylate present in the spray-drying mixture, is can improve the physical properties of the granules produced so that they become more absorbent to liquids, such as liquid nonionic detergent, which can be sprayed on them afterwards. However, zeolite and bentonite components of base grains have also been found to promote liquid absorption, and the polyacrylate 30 also promotes faster drying, thereby increasing the flow rate of the tower.

After drying, the product is sieved to the desired size, e.g. 10 - 60 or 100 U.S. Sieve Series and is ready for application of non-ionic detergent spray on it, the granules being either warm or cooled (to room temperature). However, it will not- 8200804 - 23 -

Ionic detergent are usually at an elevated temperature such as 30-6 ° C, e.g. 50 ° C to ensure it is liquid; however, it will cool to room temperature desired to be a solid often similar to a waxy solid. Even if the room temperature of the nonionic detergent is slightly tacky, this property does not smooth the final mixture as the detergent penetrates below (or into) the grain surface. The nonionic detergent applied to moving or tumbling granules in a known manner, such as by mist or as droplets, is preferably a condensation product of ethylene oxide and higher fatty alcohol, as previously described, but other nonionics may also are employed.

The enzyme preparation (herein referred to as enzyme, although it is recognized that it also contains a carrier material), aqueous silicate and any other powdered additive which is added afterwards, may be sprayed on the detent particles and perfume and any other liquid may be placed on a suitable point before or after addition of the powder or powders.

The spray dried base grains and the detergent mixtures prepared therefrom may contain little or no silicate from the soap mixer mixture, and in such a case silicate in solid form may be added afterwards. The subsequently added powdered silicate, if used, does not seem to react strongly with the zeolite, so that zeolite silicate agglomerations that tend to deposit on washed articles are reduced. Although in the absence of bentonite silicate, it would normally be used for its anti-corrosive effects, the present detergent compositions have not been found to corrode aluminum articles, even without silicate. Furthermore, bentonite does not adversely affect the stability of the product and in fact appears to promote retention of the grains making them resistant to crushing and pulverization during transportation and use. The presence of bentonite and / or polyacrylate significantly improves the properties of the final detergent mixture with the bentonite providing higher calcium ion binding rates and less zeolite being deposited on washed fabrics. When the low molecular weight polyacrylate is present, the grains become more porous and more absorbent - 2U - they absorb the non-ionic detergent in the liquid state without reducing the bulk density of the product too much. Considering that bentonite is a clay and could cause deposition and gelling problems by itself, the decreased zeolite deposition and absence of gelling are surprising and important results of the present invention.

The examples below illustrate the invention. Unless otherwise indicated, all temperatures stated therein are in ° C and all parts by weight are both in the examples and in the description.

Also, when given weights and weight ratios of zeolite, they are intended for the normally used hydrate because it is believed that the hydration water of the zeolite does not leave the zeolite and does not become part of the aqueous solvent medium in the present soap mixing operations and also because some of the the base granules and the detergent mixtures present water is present as hydration water of the zeolite.

Example I

A ^ 536 kg batch of soap mixer mixture for spray drying to base granules according to the invention and conversion to a detergent mixture is prepared by adding to the soap mixer 1832 kg of deionized water at a temperature of about 27 ° C and then at a low mixing speed 51.3 kg of anhydrous magnesium sulfate (105.5 kg of epsom salts can be used instead where the water initially introduced will be reduced to 1777 ^ kg), 12.7 kg of citric acid, 57.6 kg of Tinopal 5BM Extra Gone . (CIBA-Geigy), 68 kg ultramarine blue powder, 109.6 kg Thixo-Jel No. 1 (bentonite), 91 ^ kg Linde-hydrated zeolite kA (20% crystallization water), 636.9 kg sodium bicarbonate and U56.3 kg sodium carbonate ( soda ash) are mixed.

The mixing speed is then increased to high (in some cases it can be increased to moderate speed at an earlier time if the mixture does not mix as well as desired) and 189.6 kg of sodium silicate with the NagO: SiOg ratio of 1 : 2, k are mixed (as 399.2 kg of a ^ 7.5 ^ s aqueous solution). Mixing of the entire batch is then continued for about 1 hour (some cases may even be mixed for k hours) during which time about 90.7-272.2 kg of water may be lost through. evaporate, which water can be added if necessary. During the mixing time, the soap mixer suspension is continuously mobile and does not gel, does not set or does not set. Since bicarbonate partially decomposes to carbonate during spray drying, the amounts thereof can be varied depending on the spray drying operation characteristics.

Beginning after about 5 minutes after all the components of the soap mixer mixture are present, the mixture is brought from the mixer into a pump, which it enters at a pressure of about 21 kg / cm.

top of a countercurrent atomizing tower in which the initial temperature is at about U30 ° C and the final temperature at about 105 ° C. The substantially inorganic base granules obtained have a bulk material

O

density of about 0.6-0.7 g / cm, an initial adhesion of about 15 h0%, a particle size mainly between 10 and 100 mesh U.S. Pat. Sieve

Series (they are mixed on such a range) and with a fine (by US Sieve Hbi'5-) content of about $ 15 · The moisture content of the grains is about $ 7 · The base grains are found to be free-flowing, not tacky , satisfactorily porous, adheres strongly to their surfaces and can readily absorb significant amounts of liquid nonionic detergent without becoming questionably tacky.

Detergent products are made from the spray dried granules by spraying on their tumbling grain surfaces 25 a normally waxy nonionic detergent, either Neodol 23-6.5 or Neodol 23-7, in a heated liquid state in an amount such that a final product is obtained containing 20% nonionic detergent and proteolytic enzyme (Alcalase) is applied in powder form resulting in a 1.99% concentration in the product. The fragrance is sprayed on the product to obtain a 0.25% concentration therein. The detergent products obtained

O

have a bulk density of about 0.7 or 0.8 g / cm and contain 27.3% zeolite (hydrated), 20.1% nonionic detergent, 17.8% sodium carbonate (some of which is obtained by decomposition of sodium bi-35 carbonate), 12.7 $ sodium bicarbonate, 5.6 $ sodium silicate, 5.5% water, 8200804 - 26 - 2.0 $ enzyme, 1.7 $ fluorescent brightener, 1.5 $ magnesium sulfate .0, k $ citric acid (in citrate form), 0.25 $ fragrance, 0.2 $ ultramarine blue, 5.0 $ bentonite (Thixo-Jel). The detergent prepared from the above composition is an excellent solid detergent for washing under severe conditions and is particularly suitable for washing household washing in an automatic washing machine. It is physically and aesthetically advantageous and attractive in that it is not dusty and is particularly free-flowing, enabling it to be packaged in narrow-minded glass and plastic bottles from which it flows easily for delivery.

The detergent mixtures of the invention containing bentonite as described have a significantly improved calcium ion binding rate but more importantly they leave less residue on washed goods (in an automatic washing machine at conventional concentrations for such product and at normal washing temperatures) than similar ones. like compositions not containing bentonite. This difference is more pronounced if the wash water has a high hardness, e.g. 200 ppm as calcium carbonate, the water is cold and a gentle rinse cycle is applied.

In a control test, base grains are prepared in which the bentonite is omitted from the soap mixer mixture, and is replaced by equal amounts of sodium carbonate and sodium bicarbonate with the total of the added materials equal the weight of the replaced bentonite. The soap mixer mixture is spray dried and converted into a detergent mixture in the same manner as for the preparation of the invented detergent mixture. Such a control product, while suitable as a detergent, results in more deposited residue on washed goods than in the experimental product of the invention and has a lower calcium binding capacity. Likewise, when the silicate content in the control beads 30 is increased to 10.7% with the sodium carbonate and sodium bicarbonate concentrations being reduced to compensate for the silicate increase, the residue deposit is as bad as in the control.

According to normal methods, soap mixer mixtures can be prepared quickly and emptied from the soap mixer just as quickly, sometimes in a 5 minute period, and pumped from the soap mixer in only 10 minutes. However, it is often important that the present compositions be able to remain in the soap mixer for at least 1 hour without gelling or solidification because stagnations of these periods of time are sometimes encountered in technical production. The soap mix mixture described can be maintained for hours and often considerably longer without gelling or solidifying, which is now partly attributed to the magnesium sulfate and citric acid content as processing aids therein. However, other processing aids intended to prevent gelling and settling of the soap-mixer mixtures may be substituted and under some circumstances the amounts thereof may be reduced and one or both omitted. Likewise, other minor components of the soapmix mixture, such as the fluorescent brightening agent and pigment, can be omitted therefrom and enzyme and fragrance can be omitted from the final product, although it is highly preferred that all materials be present. The soap mixer mixing temperature can be changed e.g. by increasing to 52 ° C and the amounts of the various components can be changed + 10%, + 20% and + 30% while still remaining within the ranges previously given and processable soapmix mixtures giving the desired granules and detergent mixtures will be obtained.

Instead of using anhydrous magnesium sulfate, an equivalent amount of epsom salts can be substituted and various other components can be added as aqueous solutions, provided the amounts of moisture added with them are subtracted from that added to the soap mixer brought. Other sequences of addition can be used, but usually it will be desirable that the processing aids are added early in the manufacturing process and the silicate is added last or towards the end thereof. For the use of zeolite bA, zeolites X and Y can be substituted like other types of zeolite A. Although it is preferred to use the hydrated zeolite kA of this example, different degrees of hydration of the zeolite are acceptable and in some cases virtually anhydrous crystalline zeolites or amorphous zeolites 8200804-28 are used. Varying the amount of bentonite within the stated range to 3 # and 10 #, for example, still provides useful products, but those containing larger amounts of bentonite will usually be more effective in preventing zeolite deposits on laundry.

However, the amount used technically depends on a number of factors and will normally be a balance between the desired reduction in zeolite residue and the desired builder degree and other functional effects of other detergent mixture components. Example II

A product such as that of Example 1 is prepared but with the addition of low molecular weight polyacrylate (molecular weight = 1,000-2,000) added in the soap mixer mixture - early in its production for the bentonite, to obtain a similar product containing 1% polyacrylate. (Alcosperse 107D). The only change in composition 15 to compensate for the addition of the polyacrylate is a decrease in the sodium bicarbonate content in the soap mixer mixture of equal weight. Furthermore, the load is made smaller using a pilot factory soap mixer. The base grains supplied by the spray drying, which is carried out in the same manner as described previously in Example I, are converted into a final detergent product of the same type as in Example I except for the addition of the polyacrylate. The mixture is tested and its properties observed. It was found to be an excellent free-flowing detergent with less zeolite residue on washed laundry than controls of the types mentioned in Example 1. Furthermore, the presence of the Alcosperse noticeably improves the absorption properties of the granules produced so that they do not liquify more readily. absorb ionic detergent, which may be of the ethoxylated alcohol type or other types disclosed in the specification. However, the bulk densities of the granules and of the product are not significantly reduced, which is significant for preparing a concentrated particulate detergent of relatively high bulk density. It has been observed that when the disclosed polyacrylate is present in the soap mixer mixture, better spray drying properties are obtained and less material is lost through deposition on the spray tower walls, which advantages of advancement are important for accelerating technical production and in avoiding waste and reprocessing less-quality material.

As in Example I, the amounts of the components 5 in this Example can also be varied within the limits specified in the description to obtain base grains and detergent mixtures with improved properties. Although about 1% of the disclosed polyacrylate is found to be an optimal amount for use in the detergent compositions, 0.1-2% thereof will have good effects with greater porosity improvement of the granules being obtained when larger amounts are used. Thus, instead of 1%, 0.5 and 1.5% are also desired amounts of the polyacrylate. In some instances, it may be desirable to have higher molecular weight polyacrylates within the given limits, e.g. ^ 000 - 5000 to use but 15 in most cases the smaller part of the area will be preferred. As in Example I, in some cases processing aids, fragrance, enzyme, fluorescent brighteners and pigment may be omitted or modified, but under all those conditions the zeolite, carbonate, bicarbonate, silicate and bentonite mentioned will be present together with polyacrylate in the stated amounts in the base granules and nonionic detergent will also be present in the final detergent mixture which is like the other of the non-phosphate type.

Example III.

Detergent base granules containing 23.37 $ sodium carbonate, 16.60% sodium bicarbonate, 3 ^ 7 ^ $ zeolite kk, 13.6U $ sodium silicate (NagO: SiO ^ ratio of 1: 2, h) are prepared using pilot plant installations. ), 0.26% Ultramarine Blue, 2.20 $ Tinopal 5BM Extra Cone. (CIBA Geigy), 1.95% magnesium sulfate, 0.32 $ citric acid 30 (present as sodium citrate), 1.29% molecular weight sodium polyacrylate in the range 1000-2000 (Alcosperse 107D), and 53èb% moisture. Such a product is prepared by spray drying a pilot plant soap mixer batch containing 50% solids and 50% water including water added with the aqueous silicate solution, with the polyacrylate (as when an aqueous solution thereof such as 8200804-30).

Alcosperse 107 is used) and with epsom salts when used.

The other solid components comprise the other 50% of the soap mixer and are present in the same proportions as mentioned with respect to the base grains except for the sodium carbonate and sodium bicarbonate in which cases one third of the bicarbonate decomposition 2 parts, 90 parts of sodium bicarbonate (proportional) and 17.8 parts of sodium carbonate (proportional) are used. The water introduced into the soap mixer is deionized water and is at a temperature of 27 ° C. The loaded magnesium sulfate is anhydrous, although an equivalent amount of epsom salts can be used instead. After addition of the water, the magnesium sulfate, citric acid, Tinopal 5BM Extra Conc., Ultramarine blue powder and Alcosperse 107D are added to the soap mixer, the mixer operating at a relatively slow speed, after which the Linde hydrated zeolite kA (20% crystallization water), sodium bicarbonate and sodium carbonate can be added with the mixer at slow or moderate speed. The mixing speed is then increased to high and the sodium silicate is added as a 47.5 # aqueous solution. Mixing of the entire batch is then continued for about 1 hour (in some cases even U hours can be mixed) during which time a significant amount of water, sometimes 2-6%, can be lost by evaporation. Such water can be added if necessary. During the mixing time, the soap mixer slurry is continuously mobile, gelling, settling or caking.

Because the bicarbonate decomposition can vary depending on the spray drying conditions, the loaded amounts of bicarbonate and carbonate can also be varied accordingly to obtain the desired base grain mixture.

Starting about 5 minutes after all the components of the soap mixer mixture are present, the mixture is passed from the soap mixer to a pump, which pumps it with a pressure maintained at about 21 kg / cm in the top of a countercurrent spray tower, where the initial temperature is about ^ 30 ° C and the final temperature is about 105 ° C. The substantially inorganic base grains 35 obtained have a bulk density of about 0.6-8200804-31-0.7 g / cm, low adhesion, have a particle size range generally between 10 and 100 mesh U.S. Pat. Sieve Series (they are sieved in this area) and do not contain an objectionable amount of fine material. The moisture content of the granules is about 5%. The base granules 5 appear to be free-flowing, non-tacky, satisfactorily porous and yet have the desired physical strength and are capable of easily absorbing increased amounts e.g. 2-5 $ more, liquid non-ionic. detergent that is sprayed on it without becoming questionably sticky.

Subject to the desired properties of the prepared base grains, it is noted that the accumulation of product on the interior walls of the sputtering tower is less, often about 20-50% less, than when the polyacrylate is not present in the composition. The flow rate of the tower has been increased and it appears that the content of fine material.

15 of the product has decreased. The reduction of accumulation and production of fine material results in a significantly lower amount of required recirculation.

Detergent products are made from the spray dried granules by spraying onto the tumbling grain surfaces thereof a normally waxy nonionic detergent, either Heodol 23 - $ 5.5 or Neodol 23-7 in a heated liquid state, in such an amount that a final product containing 20.7% nonionic detergent and proteolytic enzyme (Alcalase) is applied in powder form to obtain a 1.32% concentration in the product. Fragrance is sprayed on the product to obtain the 0.25 $ concentration therein. The resulting detergent products have a bulk density of about 0.7 g / cm and contain 27.0 $ zeolite (hydrate), 20.7 $ nonionic detergent, 18.17 $ sodium carbonate (some of which is formed by decomposition of sodium bicarbonate), $ 12.9 sodium bicarbonate, $ 10.6 sodium silicate, $ 39 moisture, $ 1.32 enzyme, $ 1.71 fluorescent brightener, $ 1.51 magnesium sulfate, $ 0.25 citric acid (in citrate form), $ 0.25 fragrance, $ 0.2 ultramarine blue and $ 1.0 sodium polyacrylate. The detergent obtained from such a mixture is an excellent laundry detergent for harsh conditions and is particularly suitable for washing the household laundry in an automatic washing machine. It is physically and aesthetically advantageous and attractive in that it is not dusty and very free-flowing, so that it can be packaged in narrow glass and plastic bottles from which it flows easily for delivery. In comparative tests against similar blends that do not contain polyacrylate, the blends of the invention have been found to better remove stains and dirt when tested on different soils and stains on a wide variety of test fabrics including cotton, polyester cotton blends, polyesters and other synthetic blends. materials. With regard to stain removal, it has often been found that the polyacrylates are often more effective against stains than larger amounts of more expensive enzymes, which are often more specific for stain removal and therefore not as effective, against combinations of stains found in many wash loads. Blend 15 according to the invention containing the polyacrylate also exhibits excellent anti-redeposition effects preventing wax soiling by redeposition of removed soil.

The processes of preparation may be as those described in Example I and various processing aids and additives may be used as stated in that Example. Also, certain additives can be omitted as mentioned in Example 1. The soap mixer mixing temperature can be changed as by increasing to 52 ° C, and the amounts of the different components can be varied + 10 #, + 20 #, + 30 #, while they still remain within the previously given limits, and active soap mixes resulting in the desired granule and detergent mixes will be obtained. Different compounds can be added as aqueous solutions, provided that the added amounts of moisture are subtracted from the amount in the soap mixer recipe. Other sequences of addition can be used. Instead of zeolite kA, the zeolites X and Y can be substituted, as well as other types of zeolite A. Although it is preferred to use the hydrated zeolite kA of this example, different degrees of hydration of the zeolite are acceptable and in some cases substantially 35 anhydrous crystalline zeolites or amorphous zeolites are used.

8200804 »f -33.-

Changing the amount of polyacrylate within the given range to 1.0 and 1.7 # in the base beads results, e.g. still in useful products but those containing larger amounts of the sodium polyacrylate will usually be more effective in cleaning, absorbing nonionic detergent and promoting improved tower processing. It is usually not desirable to use more than about 2% of the polyacrylate because its effectiveness decreases at higher concentrations and the benefits obtained are not economically desirable.

10 Example IY

A product such as that of Example III is prepared but using Alcosperse 107, a sodium polyacrylate solution in which the polyacrylate has a molecular weight of about 1000 or 1000-2000 and which is a clear amber liquid with 30% solids content. The amount of Alcosperse 107 used is equivalent in solids content to the Alcosperse 107D used in Example I.

Instead of Alcosperse 107, proportional amounts can be substituted on a solid basis of Alcosperses 10 ^ (25 $ solid) and 1U9 (1 + 0 # solid content) but the results with the 107-type 20 product are better and therefore the Alcosperse 107 is preferred. No other significant changes are made to the composition compared to Example III nor to the treatment method.

The base granules from the spray drying of the soap mixer mixture are reacted according to the method described in the final product using Neodol 23-6.5 as the non-ionic detergent. The product prepared, when using Alcosperse 107, is an excellent non-phosphate detergent, suitable as a builder heavy duty laundry detergent, effective against a wide variety of stains, including liquid cosmetic "make-up" and synthetic sebum (Spangler type) A ten-member test panel also clearly prefers such a product over a similar product from which the Alcosperse 107 has been omitted. Similarly, this preference is indicated by instrumental determinations of washed materials. on cotton, dacron cotton, and nylon fabrics, and the 8200804 4 * - 34 test conditions include machine washing in 150 ppm hardness water with a detergent mixture concentration of 0.07 wt% and with a water temperature of 1 * 9 ° C. '

The same processing advantages stated in Example III are observed, including excellent dispersion of materials in the soap mixer and clean spraying of the product. The basic granules have a measurably greater porosity than control granules (minus polyacrylate). However, the bulk density is no more than a few percent, e.g. 3 $, which is important for such concentrated products. Similar results are obtained by varying the composition contents of the various other essential components + 15 $ and + 30 $, the amounts remaining within the prescribed limits. Also such results are available when other zeolites A are used with different hydration-15 degrees e.g. 15 and 22 $, and used as polyacrylates within the molecular weight range of 1000-5000. Preferably, those polyacylates with sodium, neutralized, can be used in whole or at least about 50% but less neutralized.

Similar results to those reported here can also be obtained when fluorescent brighteners, fragrance, enzyme and processing aids (citric acid, magnesium sulfate) are omitted, but in these cases care must be taken to spray dry soon after preparation of the soap mixer mixture so that this mixture does not settle in the soap mixer.

Also, as is clear, the individual contributions of the omitted materials will be lost, but the product will still be a good laundry detergent as described, the soap mixture will be well dispersed and can be dried easily, and the base grains will have an improved porosity.

30 Example V

A U536 kg batch soap spray mixture for spray drying base grains of the invention, which do not contain water-soluble silicate, is prepared by adding a soap mixer of 2132 kg deionized water at a temperature of about 2T ° C and subsequently and initially at low mixing speed in the soap mixer add 8200804 - 35 - Uj, 2 kg Tinopal 5BM Extra Conc. (CIBA-Geigy), 5.9 kg ultramarine blue powder, 3.2 kg sodium polyacrylate (Aleosperse 10ΤΏ), 951.5 kg Linden hydrated zeolite bk (20% 1 s crystallization water), 283.5 kg Thixo-Jel lo.l (bentonite), 71 ^, ^ kg sodium bicarbonate (industrial grade), 351.1 kg sodium carbonate (natural soda ash) and ^ 1.3 kg titanium dioxide (Anatase). During the mixing of the different components the mixing speed is increased to moderate and finally tet high and after all the ingredients have been added, which takes about 15 minutes xn, the mixing is continued for about 1 hour (in some cases even k hours can be mixed), during which time some of the water present, e.g. about 90.7-272.2 kg may be lost through evaporation and possibly supplemented. During mixing, the soap mixer suspension is continuously mobile and does not gel, nor does it settle or cake together. Since bicarbonate partially decomposes to carbonate during spray drying, the. amounts of bicarbonate and carbonate in the soap mixer composition are varied depending on the process characteristics of the sputtering tower.

Starting about 5 minutes after all the components of the soap mixer mixture are present, the mixture is pumped into the top of a counter-current atomizing column with a pump at a pressure of about 21 kg / cm in which the initial temperature is about ^ 30 ° C and the final temperature about 105 ° C. The substantially inorganic base granules obtained have a bulk density of

O

About 0.6-0.7 g / cm, an initial adhesion less than 10%,. and have a particle size range generally between 10 and 60 mesh, U.S. Pat. Sieve Series (they are sieved on such a path) and a fine characteristic (by U.S. Sieve 50.50) of about $ 15. The moisture content of the granules is in the range of 1 - 10 $. The base beads 30 have been found to be free-flowing (80 $ Ts flow rate), non-tacky, satisfactorily porous, yet firm on their surfaces and capable of easily absorbing significant amounts of liquid nonionic detergent without becoming objectionably tacky.

Detergent products are prepared from the spray-dried granules by spraying onto the tumbling grain surfaces thereof of a normally waxy nonionic detergent. Lieodol 23-6.5 is used, but Leodol 23-7 or Neodol 25 -7 can replace this The nonionic detergent is in heated liquid state 5 (at a temperature of about 5 ° C). The amount sprayed on is such that a final product is obtained which contains about 20% nonionic detergent Proteolytic enzyme (Alcalase) is applied in powder form, resulting in an approximately 1.5% concentration in the product and fragrance is sprayed on the product to obtain a 0.25% concentration therein The resulting detergent mixture

O

seis have a bulk density of about 0.7-0.8 g / cm and contain 32.5 $ zeolite (hydrated), 19.7 $ of the nonionic detergent, 18.5 $ sodium carbonate (some of which was obtained by decomposition of sodium bicarbonate), 13.5% sodium bicarbonate, $ 1.3 free water, $ 1.3 enzyme, $ 1.6 fluorescent brightener, $ 0.25 fragrance, $ 0.2 ultramarine blue, $ 9S6 bentonite (Thixo-Jel), 0.1% sodium polyacrylate and 1.1% titanium dioxide. The detergent prepared with the above composition is an excellent heavy duty laundry detergent suitable for washing the household laundry in automatic washing machines. It is non-dusty and very free-flowing. Detergent mixtures such as those of this example, which contain bentonite as described, appear to have a significantly improved calcium ion binding capacity, but more importantly, they release less zeolite residue on washed laundry in an automatic washing machine, especially when such laundry was line-dried as similar mixtures containing less bentonite and base granules dried by spray spray with sodium silicate. This difference is amplified if the wash water has a high hardness of e.g. 200 ppm, when calcium carbonate, the wash water is cold and a gentle stirring cycle is used.

Methods of preparation, with variations as described in Example I can be followed and certain additives omitted as stated therein. The amounts of the different components can be varied + 10 $, + 20 $ and + 30 $, while maintaining within the previously indicated areas, while processable soaps- 8200804 - 37-

mixer mixes are obtained resulting in the desired granules and detergent mixes. The solid contents of the soap mixer mixtures can be varied over the stated range, e.g. up to k5% and 65 $ while obtaining good mixing and spray drying. Instead of using zeolite bA, zeolites K and Y can be used

be substituted like other types of zeolite A. Although it is preferable to use the hydrated zeolite kA of this example, various degrees of hydration of the zeolite are acceptable and in some cases substantially anhydrous crystalline zeolites or amorphous zeolites can be used. When changing the amount of bentonite within the given range, e.g. Up to 10 and 11%, useful products are still obtained, but those containing the greater amounts of bentonite will usually be more effective in preventing zeolite deposits on laundry.

The improvement noted in the sparingly soluble silicate or non-silicate detergent mixtures of the invention, which deposit less residue on washed laundry, is confirmed by testing the product described against a control product essentially the same composition in which no bentonite is present and which -20 spring contains 6% sodium silicate. In such an evaluation, a washing machine of the Whirlpool Suds Save model is used, for washing periods of 8 minutes with a light washing cycle. The detergent mixture concentration is 0.06 $, the wash water is of mixed calcium and magnesium hardness with a total of 200 ppm hardness, as calcium carbonate, and the temperature of the water is 2k ° C. The washed items are: 100? » cotton; 100 $ polyester; 85 $ acetate and 15 $ nylon; and $ 65 polyester and $ 35 cotton. The wax is observed wet and after line drying. In neither of these cases is a residue observed. When the detergent mixture with the control composition 30 is tested, moderate residue deposits are observed on all test pieces.

The results of the above-described practical deposition test are verified by weighing residue deposited on a denim test material. In such a test, the detergent mixture according to the invention is filtered through a sample of denim material, 8200804-38 - with the detergent in solution suspension is 0.12 # 's concentration in 200 ppm (as CaCO3) hardness water he 2k ° C. The weight of the residue deposited on the cloth is noted and compared with that of a control test. test, the amount of residue compared to the control is about 75%, which is considered an important improvement.

The aforementioned adhesion test, which measures the tackiness of detergent products, is one in which 10 g of basic granules (or in some cases detergent mixture) are evenly placed between two watch glasses, both of which have a diameter of about 23 cm. with a weight of 500 g on top of the top watch glass (both watch glasses have the concave side facing up). After the assembly has stood for about 5 minutes, the weight and the top watch glass are removed and the bottom watch glass inverted, after which the product which adheres to such a watch glass is weighed. The percentage of adhesion is the number of grams of product remaining on such a watch glass divided by 10 and multiplied by 100.

The flow index is that resulting from a flow test 20 in which the volumetric flow rates of base grains (and in some cases final product) and standardized Qttawa sand (-20 +60, US Sieve Series) are compared by determining the times ndcüg for full emptying a 1.9 liter mason crumb through a 2.2 cm diameter hole in a nozzle attached to its cap 25. The index is the time for the sand flow divided by the time for the test expressed as a percentage.

Example VI

The test of Example V is repeated on a reduced scale without the polyacrylate being present in the soap mixer mixture. The speed of passage through the sputtering tower is greatly reduced and the ability of the base granules to absorb nonionic detergent is also less (or the product prepared is slightly more tacky when the same amount of nonionic detergent is applied). However, the soap mixer mixture in the soap mixer does not freeze, the base granules can be manufactured by spray drying and the resulting detergent mixture, although lower in non-ionic detergent content, b. v. Y% nonionic detergent, for maintaining flowability and non-tacky properties, is another useful product with satisfactory flow properties.

Example VII

The method described in - Example V is repeated whereby 2% sodium silicate with Na2 <D: SiOg ratio of 1: 2, k is added to the soap mixer as a ^ 7.5 # 's solid containing aqueous solution. The prepared product does not gel in the soap mixer in conventional manufacturing methods, but it is desirable to use magnesium sulfate and citric acid as processing aids to prevent gelation or freezing when the residence time is longer than normal. Also, the prepared detergent mixture leaves more residue on washed laundry, which is more noticeable than the colors of such laundry 1? be dark.

Example VIII

The test of Example V is repeated with 5% hydrated sodium silicate powder (Britesil) being added later along with the enzyme powder. Such subsequently added silicate 20 does not appear to significantly adversely affect the zeolite deposition on washed laundry and promotes the prevention of corrosion relative to aluminum washing machine parts and promotes water softening and detergent formation.

Example IX

The procedure of Example V is repeated with only water, zeolite, bentonite, sodium carbonate, sodium bicarbonate and sodium polyacrylate being present in the soap mixture and in the base granules and with only non-ionic detergent added thereafter. The product obtained has satisfactory cleaning properties but is not commercially acceptable for aesthetic reasons because it lacks the fragrance. Also, it does not clean as well due to the absence of enzyme and does not have the bluing and brightening effects that the ultramarine blue and the. impart fluorescent material to the other compositions.

& 8200804

Claims (19)

1. Free-flowing, spray-dried base beads, suitable by applying nonionic detergent thereon, for the preparation of particulate builder containing synthetic nonionic organic detergent products, due to the presence of bentonite therein, leaving less amounts of deposit, after rinsing, on fabrics washed with such a product compared to fabrics washed with such products, from which the bentonite is omitted, comprising by weight of about 15-30% sodium carbonate, about 10-22% sodium bicarbonate, about 10 - 50% water softening aluminum silicate, about 8 - 18% sodium silicate and about 1 - 205¾ bentonite and / or about 0.05 - 25¾ polyacrylate with molecular weight in the range of 1000 - 5000. Granules according to claim 1, comprising by weight of 15 - 305¾ sodium carbonate, 10 - 22% sodium bicarbonate, 10 - 50% water softening aluminum silicate, 0 - 18% sodium silicate and 1 - 20% bentonite and / or 0.05 - 2% polyacrylate with molecular weight in the range 1000-5000. Granules according to claim 2, containing 0-3% sodium silicate and 1-20% bentonite. Granules according to claim 3, with a bulk density of 0.6-3.9 g / cm, and particle sizes in the range of Ho. 10-100 U.S. Sieve Series, in which the aluminum silicate contains hydrated water softening sodium zeolite containing 15-25 wt.% Thereof hydration water and an exchange power for calcium ions ranging from 200-100 mq. calcium carbonate hardness per g of free zeolite, the sodium silicate Na ^ S: SiO2 ratio in the range of 1: 13b to 1: 3 and the weight ratio of sodium carbonate: sodium bicarbonate in the range of about 1 to 3. Granules according to claim comprising 20-30 $ sodium carbonate, 13-22 sodium bicarbonate, 35-5 hydrated zeolite, 0 sodium silicate, 5-20 bentonite and 1-15 water, excluding the hydration water of the zeolite and in which the zeolite is sea ____— * 8200804 - in ~ let A, having an extreme mean particle size in the range of 3-12 microns, with a calcium ion exchange capacity of 250-350 mgeq / g and a hardness rate of residual hardness less than 0.01 mg / dm per dm in 10 minutes, the hentonite is a swelling clay with a swelling capacity in water of 3-15 cm / g and a viscosity of 3-30 cps at 6 # concentration of water , and a weight ratio of sodium carbonate / sodium bicarbonate is in the range of 1-2. Granules according to claim 5 which have a bulk density of 0.6 - 0.8 O 10 g / cm3 comprising 0.05 - 0.5 # sodium polyacrylate with the molecular weight in the range of 1000-5000 and wherein the bentonite is suitable Wyoming is with a swelling capacity in the range of 7 - 15 cm ^ / g and a viscosity in the range of 8 - 30 cps at 6 # concentration in water. Granules according to claim 2 containing 20 - kQ% water softening aluminum silicate, 12 - 12 # sodium silicate and 1 - 15 # bentonite. Grains according to claim 7, with a bulk density of 0.6-0.9 g / cm and particle sizes in the range of Ho.10 - 100 U.S. Sieve Series, wherein the alumihosilicate is a hydrated water softening sodium zeolite containing 15-25 wt.% Thereof of hydration water and an exchange capacity for calcium ions ranging from 200-100 mgeq. calcium carbonate hardness per g of anhydrous zeolite, the sodium silicate is in the H 2 O: SiOg ratio in the range of 1: 1.1 + to 1: 3 and the weight ratio of sodium carbonate: sodium bicarbonate is in the range of about 1-3. Grains according to claim 2 comprising 20 - 25 # sodium carbonate, 13 - 19 # sodium bicarbonate, 30 - 37 # hydrated zeolite, 5 - S # sodium silicate, 5-8 # bentonite and 1+ - 10 # water, excluding the hydration water of the zeolite and in which the zeolite is zeolite A 30 with an extreme average particle size in the range of 3 -12 microns, with a calcium ion exchange capacity of 250-350 mgeq / g and with a hardness depletion rate of residual hardness less than 3 0.01 mg / dm in 10 minutes, the sodium silicate is of Ua ^ O: SiOg ratio in the range of 1: 2 to 1: 2.1+, the bentonite is a swelling-35 the clay with a swelling capacity in water of 3-15 cm / g and a fish koi. 8200804 * c - k2 - density of 3-30 cps' at 6% concentration in water and the weight ratio of sodium carbonate / sodium bicarbonate is in the range of 1-2. Granules according to claim 9 with a bulk density of 0.6-0.8 O g / cm, comprising 0.1-2% sodium polyacrylate with molecular weight 5 in the range 1000-5000, and wherein the bentonite is advantageously Wyoming O bentonite is with a swelling ability in the range of 7-15 cm / g and a viscosity in the range of 8-30 cps at 6% concentration in water. Granules according to claim 2 comprising 20 - kQ% water softening calcium silicate, U - 18% sodium silicate and 0.1 - 2% polyacrylate with the molecular weight in the range 1000-5000. Grains according to claim 11, with a bulk density of 0.5 - 0.8 g / cm and particle sizes in the range of No.10 - 100 U. S. Sieve Series, wherein the aluminum silicate is a hydrated water softening sodium zeolite containing 15-25% by weight of it hydration water and having an exchange capacity for calcium ions in the range of 200-bOQ mgeq. Calcium carbonate hardness per g of anhydrous zeolite, the sodium silicate with NagO: SiOg ratio in the range of 1: 1, ¾. to 1: 3 and the weight ratio of sodium carbonate: sodium bicarbonate is in the range of about 1-3 · Granules according to claim 12 comprising 20 - 25% sodium carbonate, 13 - 19% sodium bicarbonate, 30 - 37% hydrated zeolite, 7 - 15% sodium silicate, 0.5 - 1.5% sodium polyacrylate and 3 - 10% water, with with the exception of the hydration water of the zeolite and where the zeolite is a zeolite A with an extreme average particle size in the range of 3-12 microns, with a calcium ion exchange capacity of 250 - 350 mgeq / g and a hardness depletion rate remaining hardness less than 0.01 mg / dm in 10 minutes, the sodium silicate with Na 2 O: SiO 2 ratio is in the range of 1: 2 to 1: 2, U, 30, the polyacrylate is sodium polyacrylate and the molecular weight is in the range from 1000-3000, and the weight ratio of sodium carbonate / sodium bicarbonate is in the range of 1-2. 1¾. Process for preparing base granules according to claim 1, characterized in that a soap mixture containing 1j-0 - 75% solids, corresponding to that stated in claim 1, is contained in a water-8200804 A- -p-1 * 3 - Dry medium dries by spraying and decomposes part of the sodium bicarbonate contained therein into sodium carbonate during said spray drying. A process according to claim 11, characterized in that a soap mixture containing 50-65% solids corresponding to those mentioned in claim 6 is dried by spraying in an aqueous medium and during said spray drying a part of the sodium bicarbonate present therein to decomposed sodium carbonate, and thereby • increasing the ability of the resulting granules to absorb non-ionic detergent in the liquid state due to the release of carbon dioxide and the presence of the polyacrylate. 16. A process according to claim 1, characterized in that a soap mixture containing 50-65% solids corresponding to those mentioned in claim 10 is dried in an aqueous medium by spraying, and during said spray drying a part of the sodium bicarbonate contained therein. decomposes to sodium carbonate, and the ability of the resulting granules to absorb liquid nonionic detergent increases, due to the presence of the polyacrylate. A process according to claim 11, characterized in that a soap mixer suspension with improved gelation and settling retarding properties is prepared comprising, by weight, ^ 0 - 70% solids with 6θ - 30% water at which solids content on a 100 $ s solid base about 10 - 25 $ is sodium carbonate, 15 - 30 $ is sodium bicarbonate, the weight ratio of sodium carbonate to sodium bicarbonate being in the range of 0.5-2.20 - what makes eight aluminosilicate is 5-18% sodium silicate and 0.1-2% is polyacrylate having a molecular weight in the range of 1000-5000 and said soap mixture is dried by spraying in an atomization drying tower. The detergent mixture comprising granules of claim 1, having a nonionic detergent absorbed therein so that the content of such nonionic detergent in the mixture is in the range of 8-30%. Detergent mixture according to claim 18, wherein the non-ionic 8200804 * V-kk detergent is a condensation product of 6-12 moles of ethylene oxide and a higher fatty alcohol with 12-166 carbon atoms, and the amount of the non-ionic detergent in the mixture is in the range of 15 -22 # and whatever detergent mixture also contains 0.5-3 # of an enzyme. A detergent mixture according to claim 18 comprising granules according to claim 6 having a nonionic detergent absorbed therein so that the content of nonionic detergent in the detergent mixture is in the range of 8 - 25 # A detergent mixture according to claim 18, comprising granules according to claim 8 having a nonionic detergent absorbed therein so that the content of such nonionic detergent in the mixture is in the range of 8-25 #. 22. A detergent mixture according to claim 21 wherein the non-ionic detergent is a condensation product of 6-12 moles of ethylene oxide and a higher one. fatty alcohol with 12-166 carbon atoms and any detergent mixture containing 0.5-3 # of an enzyme. The detergent mixture of claim 21 comprising granules of claim 10 having nonionic detergent absorbed therein so that the content of such nonionic detergent in the detergent mixture 20 is in the range of 8-25 #. 2k. Detergent mixture according to claim 18 comprising by weight of 13 - 28 # sodium carbonate, 8 - 18 # sodium bicarbonate, 15 - 35 # water-softening aluminum silicate, 3 - 1 ^ · # sodium silicate, 0.1 - 1.6 # polyacrylate with a molecular weight in the range of 1000 - 5000 and 25 - 30 # of a non-ionic detergent. Detergent mixture according to claim 2k, with a bulk density O of 0.6 - 0.9 g / cm and particle sizes in the range of No. 10 - 100 U.S. Sieve Series, in which the aluminum silicate contains hydrated zeolite A containing 15-25 wt.% Thereof hydration water, the sodium silicate of a NagO; SiO 2 ratio in the range of 1: 1, U to 1: 3, the polyacrylate is sodium polyacrylate with a molecular weight in the range of 1000 - 3000, the weight ratio of sodium carbonate / sodium bicarbonate is in the range of 1-2, the non-ionic detergent is the condensation product of 5-12 moles of ethylene oxide and 35 1 moles of higher fatty alcohol with 12-16 carbon atoms and which mixture contains 8200804-b5-barrel water, excluding the hydrate content of the zeolite, and which mixture is the amount components are in the ranges of 16 - 21 $ sodium carbonate, 10 - 15 $ sodium bicarbonate, 22 - 32 $ hydrated zeolite, 8 - 13 $ sodium silicate, 0.5 - 1.5 $ sodium polyacry-5 late, 3-6 $ moisture and 10 - 22 $ non-ionic detergent. 26. Soap mixer suspension having improved mixing power and pumpability, suitable for the preparation of base granules according to claim 1 according to the method of claim 1, comprising by weight k0 - 10% solids and 60 - 30% water of which solids. content on an IQ 100 $ s solid basis about 10 - 25 $ is sodium carbonate, 15 - 30 $ is sodium bicarbonate, the weight ratio of sodium bicarbonate / sodium carbonate being in the range 0.5 - 2, 20 - 20% water softening aluminum silicate, k - 18 $ sodium silicate and 0.1 - 2 $ is polyacrylate with a molecular weight in the range 1000 - 5000. The soap mixer according to claim 26 comprising on an anhydrous basis 1.5 - 2.5 $ magnesium sulfate, 0.2 - 0.5 $ sodium citrate, 0.2 - 0tk% ultramarine blue, 1.5 - 3 $ fluorescent brightener, and 0.5 - 1.5 $ sodium polyacrylate with a molecular weight in the range of 1000-3000 8200804