DE3206265A1 - FREE-FLOWING MATERIAL IN THE FORM OF HOLLOW BALLS FOR THE PRODUCTION OF DETERGENTS - Google Patents

Description

- 12 -

description

The invention relates to hollow spheres for manufacture of nonionic detergents containing builders

compositions, particularly hollow spheres of essentially inorganic nature, the sodium carbonate, sodium bicarbonate, zeolite, sodium silicate and bentonite and / or polyacrylate and capable of absorbing nonionic active detergent in liquid form, so that free

flowing, particulate, builder-containing nonionic detergent compositions are formed. the Invention also encompasses the manufacturing processes, the crutcher slurries and the detergent compositions made therefrom which have improved washing properties

and despite the presence of zeolite and silicate on the washed Materials deposit less residue.

In recent years, synthetic organic detergent compositions, the water-softening AIu-

mini-silicates, such as zeolites containing, brought onto the market. In these compositions that also contain a synthetic organic detergent active or a surfactant Contain agents, the zeolite acts as a separating agent for the calcium and as a builder for the organic detergent

active ingredient, so that the cleaning properties in particular

«■ ο ·

- 13 -

can be improved in hard water. These compositions act as a builder and as an anti-corrosion agent Addition also used sodium silicate to the aluminum parts of the washing machine, which during the washing process with aqueous Solutions of the detergent composition come into contact to protect. The silicates can also be useful in order to counteract adverse effects of the magnesium ions in the washing water, which these on the washing activity of the detergent composition can have. In addition, one assumes

- | 0 that the silicate promotes the formation of more stable hollow spheres, especially if this is done by spray drying a crutch mix of the components of the detergent composition getting produced. It is known, however, that zeolites often tend to be on the wash, which in aqueous, these

-15 cleaning media containing zeolites was washed, leave a noticeable residue, and it has been reported on various occasions that the presence of a Silicate in such a medium, together with zeolite, increases the amount of residue deposited.

Bentonite, a swelling clay, with a relatively low exchangeability for the ions that cause water hardness have already been proposed for "use in various cleaning products, such as soap bars and detergents, in which it is often used mainly as a filler

served. In some cases, however, it is claimed that he too fulfills other functions. For example, in U.S. Patent 4,166,039 stated that it aids in the formation of a homogeneous detergent slurry when using such slurries Contain phosphate (s). Usually, however, one avoids the incorporation of clays into detergent compositions, since they are insoluble and are believed to be deposited on the materials to be washed. Indeed Clay soil removal is one of the tests used to assess laundry effectiveness. Even though one had to assume that the addition of bentonite would only exacerbate the problems associated with washing laundry aqueous detergents occur containing zeolite and silicate, it was surprisingly found that the deposit problem is decreased. In addition, the binding of calcium ions is improved.

Polyacrylates, often with a relatively high molecular weight, have also been used as components of detergent compositions suggested. They are described as components of powder and slurried detergents and as Substitutes for phosphate builders in non-phosphate Detergents recommended. The polyacrylates are known to have dispersing properties and a manufacturer of these materials it has developed for use in dispersing

ι · m

- 15 -

9 «rt * I»

purposes recommended, ζ. B. to maintain the suspension of pigments in paints. It is also known that in certain aqueous media they prevent the deposition of insoluble CaI- · cium compounds as well as the redeposition of insoluble

Inhibit substances on washed laundry. Although one polyacrylates has already been incorporated into detergent compositions, the present crutch mixes are composed of hollow spheres produced for them, as well as the detergent compositions. It has been found that the very low Amount of a certain type of polyacrylate in the specified Formulations interacts with the other components of these formulations and results in an improved product with increased Cleaning effectiveness leads. This product can with

practically feasible measures are established. 15th

The free-flowing hollow spheres according to the invention to which nonionic detergent active substance can be applied for absorption in order to produce particulate, builders containing, synthetic nonionic organic detergent products

with improved washing properties to get that after after rinsing leave less debris on fabrics washed with these products, contain about 15 to 30% by weight sodium carbonate, 10 to 22% by weight sodium bicarbonate, 10 to 50% by weight of aluminum silicate as a water softener,

0 to 18% by weight sodium silicate and 1 to 20% by weight bentonite

and / or 0.05 to 2 wt.% polyacrylate having a molecular weight from 1000 to 5000. These products normally contain 1 to 15% by weight moisture and can be used in organic detergent compositions be transferred, in_dem one located in the liquid state nonionic detergent active substance applies, which is absorbed, so that a free-flowing product is formed. Usually such a stake of the detergent active used that the final detergent Contains about 8 to 30% by weight of active detergent. Against-

^ ⁰ · wart of the polyacrylate increases the absorption capacity of the hollow spheres for the liquid nonionic detergent. Spray drying is also often improved so that less material sticks to the walls of the dryer, which reduces the throughput speed through the spray dryer.

"^ nungsturm increased and the number of cleanings required is decreased.

The various components for the hollow spheres according to the invention are usually solid with the exception of water,

although, when put in the crutcher, some in the form of hydrates or dissolved or dispersed in an aqueous medium, such as water. The sodium bicarbonate is anhydrous and the sodium carbonate is generally used in the form of calcined soda. If

wishes, however, the carbonate hydrates, like that

** »<* et« »« ft «·» ft 9 ρ «· **

- 17 -

Monohydrate can be used and in some cases other carbonates and bicarbonates, such as other alkali metal salts, e.g. B. potassium salts can be used in place of at least a portion of the sodium salt, although the sodium salts are preferred. The silicate, if present, is usually added to the crutcher as an aqueous solution having a solids content of usually 40 to 50 %, for example 47.5 % , preferably towards the end of the mixing process. The silicate used usually has a Na _? O: SiOp ratio from 1: 1.4 to 1: 3, preferably from 1: 1.6 to 1: 2, 4 or 1: 2.6 and in particular from 1: 2 to 1: 2.4. Although sodium silicate is preferred, some of the sodium silicate can be replaced with potassium silicate or other suitable soluble alkali metal silicate salt.
15th

The zeolites used include both natural and synthetic crystalline, amorphous and mixed crystalline amorphous zeolites, which contain the calcium hardness ions in the washing water satisfactorily quickly and sufficiently effectively counteracts

works. Preferably, these materials can react sufficiently quickly with the calcium ions that they alone or in conjunction with other softening agents in the detergent soften the washing water before these ions with other components of the synthetic organic detergent

can enter into adverse reactions by means of. The use

- Τδ -

Deten zeolites can be characterized as those which have a high exchange capacity for the calcium ion, normally from about 200 to 400 or more mg equivalents of calcium carbonate hardness per g of aluminum silicate, preferably from 250 to 350 mg equivalents per g. They also preferably have a softening speed to a residual hardness from 0.02 to 0.05 mg CaCO “/ l in one minute, preferably from 0.02 to 0.03 mg / l and less than 0.01 mg / l in 10 minutes, all based on anhydrous zeolite.

While other ion-exchanging zeolites can be used, those normally work for those of the present invention Purpose used finely divided synthetic zeolite builders the formula

(Na ₂ O) _x . (Al ₂ O ₃ ). (SiO ₂ ) _e.g. H ₃ O,

in which χ = 1, y = 0.8-1.2, preferably about 1, ζ = 1.5 - 3.5, preferably 2-3 or about 2 and w = 0-9, preferably 2.5-6.

The zeolite should be a monovalent cation exchange zeolite, i.e. an aluminum silicate of a monovalent Cations, such as those of sodium, potassium, lithium (if possible) or another alkali metal, ammonium or hydrogen

(sometimes). The monovalent cation is preferably the one used Zeolite is an alkali metal cation, especially sodium or potassium and especially sodium.

Crystalline types of zeolite that are at least partially considered good Ion exchangers which are useful according to the invention include zeolites with the crystal structures A, X, Y, L, mordenite and erionite, of which types A, X and Y are preferred. Mixtures of these molecular sieve zeolites can also be used especially when zeolite A is present. These crystalline zeolite types are known and in particular in "Zeolite Molecular Sieves" by Donald W. Breck, John Wiley &. Sons, 1974. Typical commercially available Zeolites with the aforementioned structures are currently belle 9.6 listed on pages 747 to 749 of the aforementioned book. Some of these and other suitable zeolites are in a number of those published in recent years as builders for detergent compositions Patent specifications described.

- The zeolite used in the invention usually consists made of a synthetic zeolite and is often characterized by a network of pores of essentially equal size in the range of about 0.3 to 1.0 nm, often characterized by about 0.4 nm (normal), where this size is based on the unit structure of the zeolite

crystal was determined. Type A or one is preferred structure similar to that described in particular on page 133 of the above-mentioned book. Good results have been achieved with a 4 A zeolite molecular sieve in which the monovalent cation of the zeolite is sodium and the pore size of the zeolite is about 0.4 nm. These zeolite molecular sieves are described in U.S. Patent 2,882,243 where they are designated as zeolite A.

The zeolite molecular sieves can be made in a dehydrated or calcined form containing about 0 or about 1.5 to 3% moisture, or in a hydrated or water-laden form containing more bound water in an amount of about 4% up to about Contains 36 % of the total zeolite weight, depending on the type of zeolite used. The water-containing hydrated form of the zeolite molecular sieve, which is preferably about 15 to 70% hydrated, is preferred for the invention when such a crystalline product is used. The production of such crystals is known. For example, in the preparation of the above-mentioned zeolite A, the hydrated zeolite crystals that form in the crystallization medium, such as hydrous amorphous sodium aluminum silicate gel, are used without high-temperature dehydration (calcination to a water content of 3% or less, which is normally

- 21 - -

Se in the production of such crackles five "catalysts, for example cracking catalysts, are used. The crystalline Zeolite is either completely barren and partially hydrated, can be obtained by filtering off the crystals from the crystallization medium and in the air at ambient temperatures

are dried so that its water content is about 5 to 30%, preferably about 10 to 25 %, such as 17 to 22 % . However, the moisture content of the zeolite molecular sieve used can be much lower than indicated above. In DIE ^"1 ^ sem case, the zeolite is typically hydrated during the mixing process and other process steps.

The zeolite should preferably be in a finely divided state having a maximum particle diameter of up to 20 µm, for example from 0.005 or 0.01 to 20 µm, preferably from 0.01 to 15 .um and in particular from 0.01 to 8 .um less Particle size, e.g. B. from 3 to 7 or 12 .um in crystalline State and from 0.01 to 0.1 µm, e.g. From 0.01 to 0.05 µm in amorphous state. Although the outermost particle sizes are much smaller, the zeolite particles usually have Particle sizes corresponding to a mesh size of 0.149 to 0.037 mm, preferably of 0.105 to 0.044 mm. Zeolites with smaller particle sizes often undesirably form dust and those with larger particle sizes

** The carbonate-bicarbonate particles can get on them during

spray drying a crutch mix to form the Hollow spheres can be deposited, do not coat sufficiently and satisfactorily.

The bentonite used consists of a colloidal clay (aluminum silicate) containing montmorillonite. Montmorillonite is a hydrated aluminum silicate, in about 1/6 of the aluminum atoms can be replaced by magnesium atoms and with varying amounts of hydrogen,

"10 Sodium, Potassium, Magnesium, and Other Metals Loosely Associated could be. The bentonite clay which has been specifically described here for the production of the hollow spheres according to the invention is called sodium bentonite (or Wyoming or Western Bentonite), which usually consists of a light-colored to

"* Consists of 5 cream-colored imperceptible powder and one in water forms a colloidal suspension with strong thixotropic properties. The clay usually swells in water 3 to 15 ml / g, preferably 7 to 15 ml / g and its viscosity in 6% concentration in water usually

to 30 centipoise, preferably 8 to 30 centipoise. Preferred Source bentonites of this type are those under the trademark THIXO-JEL from the Benton Clay Company, a subsidiary engineering bentonites sold by Georgia Kaolin Co. These materials are selective * ° mined and processed bentonites, of which the

λ ti # ♦

- 23 -

THIXO-JEL Nos. 1, 2, 3 and 4 are considered to be most useful. In a 6% concentration in water, they have a pH value in the range from 8 to 9.4, a maximum free moisture content of around 8 % and a specific gravity of around 2.6. In powdered form, about 85 % passes through a sieve with a mesh size of 0.074 mm. With these materials, the percentage of exchangeable calcium oxide is about 1 to 1.8% and that of magnesium oxide is normally 0.04 to 0.41%. Typical chemical analyzes of these materials show 64.8 to 73.0% SiO ₂ , 1.4 to 1.8% AL ₃ O ₃ , 1.6 to 2.7% MgO, 1.3 to 3.1% CaO, 2.3 to 3.4% Fe O ₃ , 0.8 to 2.8 % Na ₃ O and 0.4 to 7.0 % K O. Although these bentonites are preferred, they can be replaced by equivalent materials from other sources .

That contained in the preferred hollow spheres according to the invention Polyacrylate consists of a low molecular weight polyacrylate, usually in the range of about 1000 to 5000, preferably from 1000 to 3000 and in particular from 1000 to 2000 or about 2000. The polyacrylate can be partial or be completely neutralized: e.g. B. to about half or a third as the sodium salt. Although modified polyacrylates can be used in place of the sodium polyacrylate described, including some other alkali metal polyacrylates and hydroxylated

V ": 1-1 Γ. · ^: ·:": \ · '32 Ο6265

- 24 -

Polyacrylates, it is preferred that such a substitution is limited to a lower proportion and the polyacrylate is preferably an unsubstituted sodium polyacrylate. These materials are available from Alco Chemical Corporation under the designation Alcosperse. The sodium polyacrylates are in the form of a clear amber liquid or powder, with a solids content of the solutions of about 25 to 40%, e.g. B, 30% and a pH of the solutions or a 30% aqueous solution of the powder of about 7.5 to - \ q 9.5, z. B. about 9. These materials are completely soluble in water and are used as dispersants. They have the ability to bind calcium ions and are used to prevent the separation of insoluble calcium compounds from aqueous solutions.

The presence of the polyacrylate, even at a very low level Amount, promotes mixing of the various ingredients of the crutch mix, including that in preferred formulations used ultramarine blue, which, if it is poorly distributed, with that from the hollow spheres detergent produced can discolour washed laundry. The polyacrylate also supports the even distribution of fluorescent brighteners in the crutch mix and in the Detergent composition so that evenly white laundry is obtained. Plus, the polyacrylate does the whole

- 25 -

End product (excluding the non-ionic detergent active ingredient) more homogeneous. Auxiliaries that may be present to prevent gel formation and the deposition of inorganic substances Material in the crutch mix during the mixing process and while the mix is standing will become more uniform in the Crutch mix dispersed so that its effectiveness is improved. After all, the polyacrylate goes through that Spray drying formed hollow spheres more absorbent for the non-ionic active detergent that is sprayed onto the hollow spheres in a liquid state. In some cases it will the capacity of the beads for the detergent active ingredient improved while still remaining free-flowing. The spray-drying process is also improved because less is sprayed Material stick to the walls of the dryer

"15 remains, reducing the throughput speed through the spray drying tower increases and the number of cleanings required is decreased.

The only other material required to make the hollow spheres is water and during the Drying the hollow spheres can reduce their moisture content so that the product is virtually anhydrous. Deionized water is preferred, so that the content of hardness-causing ions can be very low and the Content of metal ions, which cause the decomposition of the

- 26 -

term hollow spheres and organic materials contained in the detergent can be largely reduced but normal city water or tap water can also be used. Usually the hardness of the Water below 150 ppm as CaCO ,,, preferably below 100 ppm and in particular below 50 ppm.

Because appropriately concentrated aqueous crutch mixes Silicate,. Carbonate, bicarbonate, zeolite as well as bentonite and / or polyacrylate in the crutcher due to interactions between the components can "freeze out" if they are held in this for an allowable time Use of silicate and thus also in the finished hollow spheres and in the detergent composition "is preferred Aids are present to prevent premature solidification or gel formation of the mixture. Most beneficial include these aids citric acid and magnesium sulfate. Instead of citric acid, soluble citrates such as sodium citrate can also be used. Although it is preferably anhydrous Magnesium sulfate is used, but various hydrates of magnesium sulfate, such as epsom salts, can also be used will. Magnesium citrate can also be used. Instead of the preferred anti-gelation system other suitable systems can be used to keep the Crutch mix in a flowable state, such as Na-

- 27 -

trium sesquicarbonate, which is part of the sodium carbonate and Can replace sodium bicarbonate.

After the production of the hollow spheres, together with the nonionic washing active substance or separately from it various auxiliaries, such as perfumes, enzymes, dyes, Bleach and flow-promoting substances are sprayed on them so that these substances do not occur during the Spray drying process are impaired and also so that their presence in the spray-dried hollow spheres not the absorption of the non-ionic washing active ingredient inhibits. However, if the auxiliaries used are stable and are usually solid, they can also be used with the inorganic ones Salts of the crutcher slurry are mixed.

so can dyes and fluorescent brighteners normally be contained in the crutchermis & ftung from which the hollow spherules are formed. The preferred dye is ultramarine blue, but other permanent pigments and Dyes can be used with it or in its place. The most preferred fluorescent brightener is Tinopal 5 BM. However, various other brighteners for cotton, e.g. B. those sometimes referred to as CC / DAS brighteners can be used from the reaction product Cyanuric chloride and the disodium salt of diaminostilbene disulfonic acid are derived, including modifications

Ι »for I *

- 28 -

with respect to the substituents on the triazine ring and the aromatic Wrestling. This class of brightener is known in the field of detergents and is mostly used when the end product does not contain bleach. If bleach is present, you can oppose these agents permanent brighteners are used. These include the benzine sulfone sulfonic acids and naphtotriazolyl stilbene sulfonic acids and benzimidazolyl derivatives. Polyamide brighteners, which may also be present include aminocoumarin

"■ 0 or dipheny lpyrazole inder i vate, and polyester brighteners that May also be present include naphthotriazolyl stilbenes. All of these brighteners are normally used in the form of their soluble salts, but they can also be added as acids will. The cotton brighteners usually contain

** 5 a larger proportion of brightener systems.

The most important of the materials that are subsequently applied to the spray-dried hollow spheres of course the non-ionic detergent active ingredient. Although

^c various nonionic detergent actives having satisfactory physical properties can be used, including condensation products of ethylene oxide and propylene oxide with one another and with bases containing hydroxyl groups such as nonylphenol and oxo-type alcohols, usually preferred as nonionic detergent actives

- 29 -

Condensation product of ethylene oxide and higher fatty alcohols. In these products the higher fatty alcohol contains up to 20 carbon atoms, preferably 12 to 16 carbon atoms and the nonionic detergent active contains about

up to 20 ethylene oxide groups per mole, preferably 6 to 12, These detergent actives are manufactured by Shell Chemical Company and are under the trade names Neodol 23-6.5 and 23-7 available.

Any desired enzyme preparation, which is also normally applied subsequently to the hollow spheres, can be used of the commercially available products, including Alcalase, (manufacturer Novo Industri, A / S) and Maxatase, which are both alkaline proteases (subtilisin).

Abigeich alkaline proteases are preferred, amylolytic enzymes such as ^ -amylase and proteolytic Enzymes are used. The compositions mentioned usually contain active enzymes together with an inert one powdery carrier, such as sodium or calcium sulfate, where

the proportion of active enzyme can vary considerably, usually from 2 to 80 % in the commercial preparations. The perfumes used, which are usually sensitive to heat, may contain volatile solvents, such as alcohol, and are usually composed of synthetic perfumes, some-

sometimes mixed with natural components, and included

"", "", # «» * «Tow« t * 4 · ** «

- 30 -

generally alcohols, aldehydes, terpenes, fixatives and other normal components of perfumes. In the present In this case, the flow properties are promoted, such as special clays, which are sometimes added to detergents because they improve their flowability and the stickiness of various types of detergents Compositions decrease, unnecessarily, possibly in part due to the presence of the bentonite and / or of polyacrylate. However, if desired, they can be added to further improve the flowability.

The proportions of the various components in the hollow spheres are such that the latter are free-flowing and the nonionic washing active substance applied in the liquid state absorb enough so that the

ten of this detergent active ingredient ultimately formed detergents is also satisfactorily free flowing. Of course The detergent made from the hollow spheres must be an effective detergent, with the existing Builders or builder salts the effect of the organic

Support washing active substances in aqueous solutions. Important is further that the product formed does not result in undesirable deposition of zeolite particles, possibly together with other substances, such as those normally soluble in water Silicates lead to the washed materials.

It has been found that reasonably satisfactory hollow

β ■ * · «

- 31 -

spheres that fulfill this purpose, in the presence of silicate 15 to 30% by weight of sodium carbonate, 10 to 22% by weight of sodium bicarbonate, 20 to 40% by weight of water-softening aluminum silicate (zeolite) 3 or 4 to 12% by weight of sodium silicate and 1 Can contain up to 15% by weight of bentonite as active components, and also 1 to 15% by weight of water. In these hollow spheres the aluminum silicate is preferably in the form of sodium zeolite with 15 to 25% by weight of water of hydration. Preferably this zeolite is zeolite A. The preferred weight ratio of sodium carbonate: sodium bicarbonate is about 1 to 3, the hollow spheres having a bulk density of 0.6 to

3 3

0.9 g / cm, preferably from 0.7 to 0.8 / cm and which Particle sizes of the hollow spheres clear mesh sizes of 2.00 to 0.149 mm, i.e. pass a sieve with a mesh size of 2.00 mm and place it on a sieve with a clear mesh size of 0.149 mm remain, preferably clear mesh sizes of 2.00 mm to 0.25 mm. Further preferred proportions of the components are 20 to 25% sodium carbonate, 13 to 19% sodium bicarbonate, 30 to 37%

2 ^ hydrated zeolite, 5 to 8 or 10% sodium silicate, 5 to 8% bentonite and 4 to 10% water, excluding the hydration water of the zeolite. In these preferred products is the weight ratio of sodium carbonate: sodium bicarbonate in the range from 1 to 2.

'.

If a polyacrylate is present in the composition for the hollow spheres together with the zeolite, its proportion normally makes up 0.1 to 2%, preferably 0.2 to 1.6 % and in particular 0.8 to 1.4 % . The proportions of the auxiliaries and the processing-facilitating agents as well as the fillers are, if these are contained in the hollow spheres, normally limited to 20 % and preferably to 1 to 10%, in particular to 3 to 7%. When using magnesium sulfate and citric acid, the proportions of the substances facilitating processing are normally 1 to 3 % magnesium sulfate, in particular 1.5 to 2.5% and 0.2 to 1% sodium citrate, in particular 0.2 to 0.5 %. The amount he ^ pigments and fluorescent brightener is preferably 0, ^v 05 to 0.6% pigments, such as ultramarine blue, and in

Particularly 0.2 to 0.4 % and 0.1 to 4 % fluorescent brighteners, in particular 1 or 1.5 to 3%. These proportions of the substances and auxiliaries that facilitate processing relate to different types of hollow spheres according to the invention, provided that auxiliaries and processing promote

modifying substances are used.

The proportions of the various components in the Crutchermixture and the hollow spheres made from it, the polyacrylate but do not contain bentonite, are of such a nature

that a uniform or almost uniform mixture is obtained

th and the hollow spheres free-flowing and sufficient absorbent for when applied in a liquid state nonionic detergent are active, so that through the incorporation of the detergent active ingredient obtained is satisfactorily free flowing. It has been found that hollow spheres 15 to 15 which are satisfactory for this purpose 30% by weight sodium carbonate, 10 to 22% by weight sodium bicarbonate, 20 to 40% by weight of aluminum silicate (zeolite) as a water-softening agent, 3 or 4 to 18% by weight of sodium silicate and 0.1 contain up to 2% by weight of polyacrylate as active components, and 1 to 12 or 15% by weight of water. The preferred weight ratio of sodium carbonate: sodium bicarbonate in the product is about 1 to 3, the hollow spheres being a bulk

3
weight from 0.5 to 0.8 g / cm, preferably from 0.7 to 0.8 g / cm and their particle sizes correspond to a mesh size of 2.00 to 0.149 mm, ie a sieve with a mesh size of 2 .00 mm and remain on a sieve with a mesh size of 0.149 mm. They preferably correspond to clear mesh sizes of 2.00 to 0.25 mm. Further preferred proportions of the components are 20 to 25% sodium carbonate, 13 to 19% sodium bicarbonate, 30 to 37% hydrated zeolite, 7 to 15% sodium silicate, 0.5 to 1.5% sodium polyacrylate and 3 to% water, the water of hydration except for the zeolite. In particularly preferred products of this type, the weight

• ft · · rr «* * Φ

- 34 -

Sodium carbonate: sodium bicarbonate ratio in the range of up to 2.

If little or no water-soluble silicate is contained in the hollow spheres to be produced, as referred to above has been given for other types of hollow spheres according to the invention, the proportions of the various components are also given selected so that the hollow spheres are free flowing and sufficiently absorbent for when in the liquid state Applied nonionic detergent active are so that that formed by the incorporation of this detergent active ingredient Detergent also released in a satisfactory manner is. It is also important that the product formed does not lead to undesirable deposition of zeolite particles, possibly together with other substances on the washed Materials leads. It is also desirable that the hollow spheres have adequate bulk density and color. It has been found that this purpose is more satisfactory Well-fulfilling hollow spheres 15 to 30% by weight sodium carbonate, 10 to 22% by weight sodium bicarbonate, 10 to 50% by weight Aluminum silicate (zeolite) as a water-softening agent, 0 to 3% by weight sodium silicate and 3 to 20% by weight bentonite as active ingredients, also contain 1 to 15% by weight of water. The percentage of water indicated means free water

² ^ and does not include the water of hydration of the zeolite.

Accordingly, the five percent includes the zeolite the water of hydration. In some cases it can be related on the free moisture content the product will be anhydrous, but these cases are very rare and it is normal- It is desirable that the hollow spheres contain at least a small amount of water in order to prevent undesirable dust formation which could otherwise occur with anhydrous formulations. The preferred weight ratio of sodium carbonate : Sodium bicarbonate in the product is in the range of about

" ¹ ^ 1 to 3, the hollow spheres having a bulk density of 0.6

3 3

to 0.9 g / cm, preferably from 0.6 or 0.7 to 0.8 g / cm and their particle size correspond to clear mesh sizes of 2.00 mm to 0.149 mm, ie a sieve with a clear mesh size of 2, 00 mm and remain on a sieve with a mesh size of 0.49 mm. They preferably correspond to mesh sizes of 2.00 to 0.25 mm. Further preferred proportions of the components are 20 to 27 % sodium carbonate, 14 to 21% sodium bicarbonate, 20 to 50% hydrated zeolite, 0% sodium silicate, 5 to % bentonite and 1 to 5% water excluding the water of hydration of the zeolite. In these more preferred products, the sodium carbonate: sodium bicarbonate weight ratio is in the range 1-2. When silicate is contained in the hollow spheres, its amount is preferably limited to 2%, and particularly to 0.5 to 1 % , others are preferred

- 36 -

Quantities of the important components according to the invention are 35 to 45% hydrated zeolite and 5 to 15 %, in particular 10 to 15%, bentonite.

If a polyacrylate is contained in the composition for the hollow spheres, its proportion is normally 0.05 to 0.5%, preferably 0.05 to 0.3% and in particular 0.1 to 0.2%. The proportion of auxiliaries and processing-promoting substances as well as fillers is, if such substances are contained in the hollow spheres, normally limited to 20 % , preferably to 1 to 10 % and in particular to 3 to 7 %, with the remaining proportions being the are the same as given above.

Although it has been found that in the inventive Detergent compositions produced with hollow spheres do not have to be present as a corrosion-inhibiting additive, which replaces the silicate, such additives can be used. Corrosion-preventing additives are preferred,

which are stable under the conditions in the crutcher and in the spray drying tower and do not interfere with these operations. The corrosion-preventing additives or antioxidants can be organic or inorganic, whereby the inorganic materials are usually preferred. They will pay particular attention to their suitability for prevention

the corrosion of aluminum parts in washing machines. If it is desired to use a silicate for this purpose or for the treatment of magnesium ion water hardness, a powdery silicate is normally preferred, e.g. B. hydrous sodium silicate, which is commercially available under the name Britesil (manufacturer Philadelphia Quartz Co. (Na OtSiO ₂ = 1: 2.4) and is added afterwards. However, other normally solid soluble silicates, preferably of alkali metals, can also be added afterwards the hollow spheres according to the invention are given, from which the nonionic detergent active ingredient has been absorbed beforehand.

If the product has fabric softening properties should, plasticizers, preferably in dry powder form, can also be added subsequently in a suitable manner to the hollow spheres are given. This class of substances is known and the plasticizers are mostly cationic compounds represent, in particular quaternary ammonium compounds such as quaternary ammonium halides. Are particularly preferred the quaternary ammonium chlorides and bromides with higher Alkyl, alkylaryl and arylalkyl-lower. alkyl groups, such as Distearyl dimethylanimonium chloride. Of the commercially available Plasticizers are most preferred to that sold under the trade name Arosurf TA-100 (manufacturer

- 38 -

Sherex Chemical Company, Inc.) These compounds also have antistatic and antibacterial properties. If desired, but other antibacterial auxiliaries can also be used, which are preferably also subsequently ^ lent to be incorporated into the product.

An important feature of the invention is that an effective detergent composition containing builders can be produced solely on the basis of a nonionic detergent active substance using a technically feasible process. Sometimes, however, it may be desirable to include an anionic surfactant or detergent in the final product, usually to add foam properties and supplement the detergency "S. It is normally preferred not to incorporate such anionic detergent in the crutch mix, so that if one or more such anionic detergent actives are used, these are preferably added subsequently to the spray-dried hollow spheres, usually after the absorption of the nonionic detergent actives in the liquid state by the hollow spheres are in powder form and / or sometimes mixed with builders, the linear higher alkyl

benzenesulfonates, higher fatty alcohol sulfates and polyethoxylated ones higher fatty alcohol sulfates are preferred. In these. * Products the higher alkyl and higher alcohol fractions normally contain 8 to 20, preferably 12 to 16 carbon ° atoms, and these detergent active substances are in the form of their water-soluble ones Alkali metal salts, preferably as sodium salts. The ethoxylated alcohol usually contains sulfate 3 to 20 moles of ethylene oxide per mole of fatty alcohol.

® The proportions of the various components in the final detergent composition can easily be calculated from the proportions given for the hollow spheres if the proportions of washing acti vst.of f subsequently added to the hollow spheres and of other materials are subtracted. If z. If, for example, the final detergent composition only contains 20% nonionic active detergent that was subsequently added, the individual proportions of the components can be calculated by adding 0.8, ie (100 -

20) / 100 multiplied. If the proportion of nonionic detergent active ingredient in formulations in which only this additive was added to the hollow spheres, 8 to 25% of the detergent composition similarly, the multiplier is 0.75-0.92. Usually the final

valid percentage of the non-ionic detergent active

8 to 25%, preferably 15 to 22% and in particular about 20% in the product. In some cases a proportion of 8 to 13% may be preferred for certain types of product. Usually the percentage of perfumes in the final product is 0.1 to 1%, preferably 0.2 to 0.4%; the percentage of enzyme 0.5 to 3 %, preferably 1 or 1.5 to 2.5%, and the percentage of flowability-improving agent that can be post-added is less than 2%, preferably less than 1%. When calculating the proportions of the components in the final composition from the amounts specified for the hollow spheres, of course, in addition to the percentage of subsequently added nonionic detergent active ingredient, the percentages of other subsequently added auxiliaries must also be taken into account. If * these subsequent additions were made in the form of aqueous solutions, this also influences the moisture content, which is often kept in the range from 1 to 12 % , but can sometimes be up to 15%.

If polyacrylate is used, but not bentonite, the proportions of the various components are 13 to 28% sodium carbonate, 8 to 18% sodium bicarbonate, 15 to 35% aluminum silicate as a water-softening agent, 3 to 40% sodium silicate, 0.1 to 1.6% polyacrylate, 8 to 30%

non-ionic detergent and 1 to 10% water. the

- 41 -

preferred ranges are 16 to 21 % sodium carbonate, 10 to 15% sodium bicarbonate, 22 to 32 % hydrated zeolite, 8 to 13 % sodium silicate, 0.5 to 1.5% sodium polyacrylate, 3 to 6% and sometimes 3 to 10% moisture as well 10 to 22 or 25% non-ionic detergent active. The percentages of processing agents, optical brighteners and colorants in the final detergent composition are about the same as in the underlying hollow spheres. They are preferably 0.2 to 0.6% for sodium citrate (from the addition of citric acid) and 1 to 2% for the magnesium sulfate, 0.1 to 0.3% for the ultramarine blue and 1.5 to 2% for the Fluorescent brightener. The enzyme content is 0.5 to 3%, usually 1 to 2 % and the perfume content is 0.1 to 1%, preferably 0.2 to 0.4%.

The proportions of the various components in the spray-dried Fraction of the final detergent composition can, if little or no silicate is present, in

^ ■ ® can be calculated in the manner described above. With regard to the components added subsequently, the percentages of nonionic detergent active are the same as given above. The percentage of perfume in the final product is 0.1 to 1 %, preferably 0.2 to 0.4 %, the percentage of

^ 5 enzyme 0.5 to 3%, preferably 1 to 2%, and if water-

containing silicate is subsequently added, its proportion normally makes up 2 to 10%, preferably 3 to 8 %, for example about 5 % . If a plasticizer is included in the end product, its proportion is usually 3 to 12 %, preferably

preferably 5 to 10 %, and if one or more anionic detergent actives are used, their amount is limited so that they do not make up more than the amount of the nonionic detergent active, the total weight of anionic and nonionic detergent active in the end product in the above for the nonionic active detergent alone is the range specified. If an anionic detergent active is used, its amount is normally 0.2 to 0.8 times the weight of the anionic detergent active. Needless to say, when calculating

the proportions in the final composition except for the percentage of subsequently added non-ionic Active detergent, the percentages of the other subsequently added auxiliaries are taken into account. If those subsequent additions were made in the form of aqueous solutions,

this also affects the moisture content. This is usually 1 to 12 % in the end product, but can sometimes be up to 15 % .

The hollow spheres according to the invention for the production of

Detergent compositions are obtained by spray drying

\ · Ί: ·! IV'i'V. ⁵ 320626? '

an aqueous crutch mix, usually about _; Contains 40 to about 70 or 75 % solids, preferably 50 to 65% and the remainder water, which, as indicated above, preferably consists of deionized water. However, city water can also be used. The composition of the crutch mixture can be calculated from the composition of the hollow spheres, taking into account the moisture content of the hollow spheres and the crutch mixture. If, for example, a Cruther mix is to contain 50% moisture and to produce hollow spheres with a moisture content of 5 % from it, ignoring the water of hydration of the zeolite, the percentages of the components in the hollow spheres should be 10/19, ie (100/2 100-5 "]). The above calculations are satisfactory when using components that do not decompose when spray-dried. However, it is known that some of the bicarbonate converts to carbonate when dried at elevated temperatures in a spray tower therefore, knowing the characteristics of the tower and drying conditions so that the degree of bicarbonate decomposition can be predicted, the required proportion of carbonate and bicarbonate in the crutch mix can be calculated, for example if one has a product with about 22% sodium carbonate "and about 16%" wants to produce sodium bicarbonate, should in cases where the spray tower e about 1/3 of the bicarbonate is decomposed to carbonate, with two parts of carbonate

- 44 -

bonat come from three parts of decomposed bicarbonate, 24% bicarbonate and 17 % carbonate (on a dry basis) are added to the crutcher.

Regarding the various formulations and calculations It must be taken into account that the zeolite in the Crutchermixture and in the spray-dried hollow spheres as well in the detergent composition up to about 20% water of hydration but the degree of hydration may vary. For consistency and calculations however, if a constant degree of hydration is assumed,

The crutch mixture, from which the hollow spheres according to the invention are most advantageously produced by spray drying, consists predominantly of inorganic materials and the content of the organic materials is usually limited to 10%, preferably 7 % and in particular 4%, based on the solids. These organic materials that may be present include citric acid compounds (citric acid and soluble citrates) fluorescent brighteners, polyacrylates, dyes, and pigments. Other organic materials can also be present including hydrotropic salts, chelating agents, and polyelectrolytes. However, the crutch mix primarily consists of inorganic materials and water.

- 45 -

For hollow spheres containing polyacrylate but not bentonite, the crutch mix typically contains about 10 to 25% sodium carbonate on a 100% solids basis. 15 to 30 % sodium bicarbonate with a sodium bicarbonate: sodium carbonate weight ratio of 0.5 to 2.20 to 40% water-softening aluminum silicate, 4 to 18% sodium silicate and 0.1 to 2% polyacrylate. When processing agents are present, their proportions are usually 1 to 3% magnesium sulfate and 0.2 to 1 % sodium nitrate on the same basis. Preferably, the sodium polyacrylate content in these crutcher slurries is 0.5 to 1.5 percent and, if processing aids and colorants are present, the amount is 1.5 to 2.5 percent magnesium sulfate, 0.2 to 0.5 % Sodium citrate, 0.2 to 0.4 % ultramarine blue and 1.5 to 3% fluorescent brightener on a solid basis.

The crutch mix is preferably made by sequentially adding the various components in such Way made to be the most miscible, easily pumpable and non-settling slurry for spray drying is obtained. The order of addition of the various components can be varied depending on the Circumstances, however, the silicate solution, if used, should

last, and if not last, at least after the encore added to the materials preventing gel formation or settling or to substances which promote processing will. It is usually preferred to add all or almost all of the water to the crutcher first, preferably at about the processing temperature, followed by processing enhancement if used Substances and other components used in smaller quantities, including pigments and fluorescent brighteners and, If used, polyacrylates are added and then, if used, the bentonite, the zeolite, the. Bicarbonate, the carbonate and, if used, the silicate. Usually each component is included in these additions the addition of the next component carefully mixed in, however the type of addition can be varied depending on the Circumstances so that joint additions are possible when feasible. Sometimes the components, like the silicate can be added in two or more proportions. Various components can be premixed before adding them to speed up the mixing process. Usually, with the added materials, the mixing speed and the mixing power increases. For example, low speeds can be achieved until after the last bentonite or zeolite has been added before, during and after the addition of the silicate solution to medium and then to high speed can be increased.

The temperature of the aqueous medium in the crutcher will usually be about room temperature or elevated temperature, usually in the range of 20 to 80 g, preferably from 30 to 75 ° C and especially at 40 to 70 ⁰ C. The heating of the Crutchermediums the solution of the water-soluble Promote salts in the mixture and thus increase the miscibility, but heating in the crutcher can also reduce the production speed and favor the settling of the mixture. The use of the processing enhancing agents ensured in the mixture that desired, not money-forming slurries are obtained both at low and at higher temperatures, temperatures above 80 ⁰ C (and sometimes 70 ⁰ C) are usually avoided, as these Temperatures of one or more crutcher

components can decompose, e.g. sodium bicarbonate.

In some cases, lower crutch temperatures also raise the upper limit for the solids content in the Crutcher, probably because usually gel-forming or

settling components are made insoluble. 20th

The crutch mix times to make good slurries can vary widely, from just 5 minutes in small crushers and with slurries with higher moisture content, up to 4 hours in some cases. The required

Mixing time for all crutch components in a medium in

- Mixing together insignificant homogeneous takes only 10 minutes Sleep up to an hour in some cases, although 30 minutes is the preferred upper limit. In consideration of of the initial mixing times, normal times in the crutcher are 15 minutes to 2 hours, e.g. B. 20 minutes to 1 hour, but the crutch mix should last for at least 1 hour, preferably 2 hours and especially 4 Hours or more after the preparation of the mixture has been completed, be mobile without gel formation or settling in it enter. She can even be mobile 10 to 30 hours before she is due to certain situations or during the Producing problems occurring is pumped into the spray drying tower.

The crutcher slurry in the various salts and the other components are dissolved or evenly distributed in particulate form, is used in the usual manner for the ■ Spray drying tower, which is usually located next to the crutcher. The slurry flows from the bottom of the crutchers to a positive displacement pump, which it presses through high pressure spray nozzles at the top of a conventional Spray drying tower, which is operated in countercurrent or cocurrent, pushes - thereby - the droplets of the slurry fall through a hot drying gas, usually the combustion products of heating oil or natural gas, in which the drip

- 49 -

32Q62-65

to the desired absorbent hollow spheres to be dried. During the drying stage a part can des bicarbonate, often 1/4 to 1/2, e.g. B. 1/3 converted to carbonate «, Whereby carbon dioxide is released, which interacts with the possibly existing polyacrylate content can improve the physical properties of the hollow spheres in the spray-dried mixture, so that this greater absorption capacity for liquids, show how liquid nonionic washing active substance, the other - | 0 can then be sprayed on it. The one in the hollow spheres contained zeolite and bentonite also seem to promote the absorption capacity for liquids, and the polyacrylate also promotes faster drying, thereby increasing throughput through the tower.

After drying, the product is reduced to the desired particle size sifted out, e.g. B. to a particle size corresponding to a mesh size of 2.00 to 0.25 or 0.149 mm, whereupon it was necessary for the nonionic to be sprayed on Active detergent is ready. The hollow spheres can be in a warm state or in a state cooled to room temperature. However, the nonionic detergent active usually has an elevated temperature, such as 30 to 60 C, e.g. 50 C, to ensure that it is liquid. When cooling on However, it is desirably solid and at room temperature

often forms a waxy solid. Even at room temperature, the nonionic active detergent is somewhat sticky. However, this property does not affect the flowability of the final composition because the detergent

substance penetrates into or below the surface of the hollow spheres. The non-ionic detergent active in the well-known Sprayed onto the moving or circulating hollow spheres or applied in the form of droplets, consists preferably of a condensation product of ethyl

Lene oxide and higher fatty alcohol, as indicated above, but other non-ionic detergent actives can also be used. The enzyme preparation, here also referred to as enzyme, although it contains carrier material, water-containing silicate as well as any other powdery ones to be added subsequently

Auxiliaries can then be dusted onto the particles. Perfume and any other liquids can be added at an appropriate time before or after the addition of the powdery Substances are sprayed on.

The spray-dried hollow spheres and those made from them Detergents can have little or no silicate from the crutch mix and in this case solid silicate can be added afterwards. The subsequently added

powdery silicate doesn't seem much when used 25

m & mm, 9 «·« * · M * Aft 49 6 «4

- 51 -

to react with the zeolite, so that zeolite-silicate agglomerates, which tend to deposit on the washed materials are reduced. Although if not bentonite is present, silicate is normally used, at least with regard to its anti-corrosive effect it was not found that the detergents according to the invention Compositions Aluminum objects corrode, even in the absence of silicate. The bentonite impaired does not affect the consistency of the product and does

" ¹ ^ contributing to the fact that the hollow spheres are held together so that they are resistant to breakage and powder formation during their transport and their use. The bentonite and / or the polyacrylate significantly improve the properties of the final detergent composition.

** 5 composition, whereby the bentonite leads to a stronger bond of calcium ions, so that less zeolite on the washed fabrics is deposited. When low molecular weight polyacrylate is included, the spheres are hollow more porous and better absorb the nonionic detergent active substance present in the liquid state without affecting the bulk density of the product is reduced in an unacceptable manner. Taking into account that bentonite is a clay, it could deposition and gelation problems are expected, so that the reduced zeolite deposition and the lack of gelatinous

"dung are surprising.

β * ο

- 52 -

The following examples illustrate the invention. Unless otherwise indicated, all mean temperatures ° C and all parts in the examples and in the description are based on weight. Those given for the zeolite Weights and ratios relate to the normal hydrate, since it is assumed that the water of hydration of the zeolite does not leave the zeolite and does not become part of the aqueous medium in the crutch mixes, and also because some water contained in the hollow spheres and in the detergent compositions as the hydrate water of the zeolite is present.

example 1

A crutch mix of 4536 kg for spray drying

to hollow spheres according to the invention and their conversion into a detergent composition is made by adding 1,832 kg of deionized water to the crutcher at a temperature of about 27 C and then 51.3 kg of anhydrous magnesium

sulfate (instead of this magnesium sulfate, 105.5 kg Epsom salts are used; in this case the water initially supplied is reduced to 1777.4 kg), furthermore 12.7 kg citric acid, 57.6 kg Tinopal 5BM Extra Cone. (CIBA-

Geigy), 68 kg ultramarine blue powder, 169.6 kg Thixo-JeI No. 25th

53 -

1 (bentonite), 914 kg hydrated zeolite "4A (Linde, 20 % Kristal." Isation water)., 636.9 kg sodium bicarbonate and 456.3 kg sodium carbonate (calcined soda). Then a high mixing speed is set (in some cases the mixing speed can be increased to a medium value at an earlier point in time if the mixing is not as good as desired) and 189.6 kg of sodium silicate are _{mixed with the Na 2} O: SiO_ -Ratio 1: 2.4 added (399.2 kg of a 47.5% aqueous solution). Then the

- ^ q entire batch mixed for about 1 hour (in some cases can be mixed for 4 hours). During this time, about 90.7 to 272.2 kg of water can be lost through evaporation which can be replaced if desired. During the mixing, the crutcher slurry is constantly agitated.

-) 5 loaned. There is no gel formation in it, no settling or Baked in. Since the bicarbonate is partially converted into carbonate during drying, its quantities can can be varied depending on the conditions in the spray drying tower.

About 5 minutes after all components of the crutch mix are added the mixture is fed into a pump

2 it leads at a pressure of about 21 kg / cm into the upper end of a spray drying tower operated in countercurrent, in which the initial temperature is about 430 ° C and the final temperature

is about 105 ^° C. The hollow spheres formed, which consist essentially of inorganic materials, have a bulk density of 0.6 to 0.7 g / ml, an initial adhesiveness of about 40 %, a particle size range of essentially a mesh size of 2.00 to 0.149 mm (they are screened out on this area) and a fine fraction, which passes through a sieve with a mesh size of 0.297 mm, of about 15%. The moisture content of the hollow spheres is about 7%. The hollow spheres formed are free-flowing, non-sticky, satisfactorily porous, but firm on their surface and are able to easily absorb substantial amounts of liquid nonionic active detergent without becoming undesirably sticky,

Detergent products are produced from the spray-dried hollow spheres by spraying a normally waxy nonionic active detergent, i.e. either Neodol 23-6.5 or Neodol 23-7 in a heated liquid state, onto the surfaces of the circulated hollow spheres in such an amount that the end product 20 % non-ionic detergent. A proteolytic enzyme (Alcalase) is applied in powder form in an amount such that its concentration in the product is 1.99 % . Perfume is sprayed on in an amount that contains 0.25 % in the product. The detergent obtained has a bulk density

of about 0.7 or 0.8 g / ml and contains 27.3% zeolite (hydrated), 20.1 % nonionic detergent active, 17.8 sodium carbonate (part of which is formed by the decomposition of sodium bicarbonate), 12.7 % Sodium Bicarbonate, 5.6% Sodium Silica, 5.45% Water, 2.0% Enzyme, 1.7 % Fluorescent Brightener, 1.5% Magnesium Sulphate, 0.4% Citric Acid (as citrate). 0.25% perfume, 0.2% ultramarine blue, 5.0% bentonite (Th-xo-Jel). The detergent obtained with the stated formulation is an excellent heavy-duty detergent

"Ό and is particularly suitable for washing household linen in automatic washing machines. It is physically and aesthetically pleasing in that it is non-dusty and extraordinary flows freely so that it can be filled into narrow necked glass and plastic bottles from which

"^ it can be easily measured. The detergent compositions according to the invention, which contain bentonite as described, show a significantly improved binding of calcium ions, but more importantly, they leave less residue on the washed laundry, which in automatic

table washing machines using the usual concentrations on detergent and at normal washing temperatures than similar compositions that does not contain bentonite. This difference is even more pronounced if the washing water has a high degree of hardness, e.g. 200 ppm as calcium carbonate, the washing water is cold

- 56 -

and a mild wash cycle is used.

For comparison, hollow spheres made from a Cruther mixture sore that did not contain bentonite. The bentonite was

* by equal parts by weight of sodium carbonate and sodium bicarbonate was replaced so that all of the added material corresponded to the weight of the omitted bentonite. the Crutch mix was spray dried and on the same Converted into a detergent composition as above leads. The "control product" proved to be a useful detergent, but left more on the washed laundry Deposits back than the product according to the invention and bound calcium to a lesser extent. If the silicate content in the control hollow spheres was increased to 10.7%, the

^ increased silicate content due to a reduced carbonate and Sodium bicarbonate content was compensated, the build-up of residues was worse than the "control product".

Usually the Crutcher mixes are quick to produce

and empty from the crutcher just as quickly. Sometimes they can be made in as little as 5 minutes and in as little as 10 Minutes pumped out of the crutcher. However, it is often important that the mixes in the crutcher are stable for at least 1 hour do not form gels or solidify, because sometimes disturbances of

such periods of time occur. The crutcher mix described can even last 4 hours and even longer in the crutcher be held without gel formation or solidification occurring, which is at least in part due to the content of magnesium sulfate and citric acid as a processing aid Is attributed to funds. However, there can also be other processing promoting and gel formation and settling preventive agents are used, and under certain conditions their proportions can be reduced and one or

'O both components can be omitted. Likewise can other components of the Cruther mixture used in smaller quantities, such as the fluorescent brighteners and pigments can be omitted, including the enzyme and perfume, although it is preferred that all materials are present. the

"15 Mixing temperature in the crutcher can be modified, ζ. B. to 52 ° C increased and the proportions of the various components can be within the ranges given above by -10%, -20% and -30% can be varied, wherein processable Crutch mixes are obtained which give the desired hollow spheres and

Lead detergent compositions.

In place of the anhydrous magnesium sulfate, an equivalent amount of epsom salts can be used, and various other components can be added as aqueous solutions, provided that the amount of moisture introduced with them

activity is deducted from that put in the crutcher. Other orders of addition can be used, but it is usually desirable that the processing promoting agents are added at an early stage of the manufacturing ^ process, and the silicate last or towards the end. Instead of zeolite 4A, zeolite X and Y can also be used, as well as other zeolite A types. While the in. hydrated ones used in the present example Zeolite 4 A is preferred, various hydration

"^ ⁰ grade of zeolite is acceptable and in some cases nearly anhydrous crystalline zeolites or amorphous zeolites can be used bigger

"* ^ Quantities of bentonite-containing products in preventing the zeolite deposit on the laundry is usually more effective. The proportion used commercially depends on a variety depends on factors and is usually in the middle between the desired reduction in zeolite residue and the desired

tem builder and other functional properties of the other Components of the detergent compositions lie.

Example 2

A product similar to that of Example 1 is produced

with the exception that at an early stage of manufacture

* 59 -

before adding the bentonite, a polyacrylate with a lower Molecular weight (1000 to 2000) added to the crutch mix to make a comparable product with a grade from 1% polyacrylate (Alcosperse 107D) to get, the only change in the formulation to the addition of the polyacrylate; to compensate consisted in reducing the Sodium bicarbonate content · of the crutch mix by the same weight. In addition, the approach was smaller. It became a pilot Plant used. The hollow spheres were spray-dried

^ q obtained, which was carried out in the same way as in Example 1, and then turned into a detergent product converted in the same way as in Example 1, with the difference that polyacrylate was added. The properties of the detergent obtained were examined. One posed

.] 5 found it to be an excellent free flowing laundry detergent acted, which left less zeolite on the washed laundry than the control products described in Example 1. In addition, the absorbency of the hollow spheres became noticeable through the presence of the Alcosperse improved so that they the liquid nonionic detergent active more easily absorbed. This can be an ethoxylated alcohol or others in the description mentioned species act. The bulk density of the hollow spheres and the detergent product was not noticeably reduced, which is essential when a concentrated in particulate

- 60 "-

form present detergent with a relatively high Bulk density is to be produced. It has also been found that when the polyacrylate described is in the Crutchermixture is present, the spray drying is better ° and less material due to deposition on the walls of the Spray tower is lost. These process advantages are important in order to accelerate technical production and reduce losses as well as the reprocessing of material inferior

Avoid quality.
10

As in Example 1, the proportions of the components can also be varied here within the limits specified in the description in order to obtain hollow spheres and detergent compositions with improved properties. While about 1% of the polyacrylate described appears to be an optimal amount in the detergent compositions, amounts of 0.1 to 2% also have good effects, the larger amounts leading to a greater porosity of the hollow spheres. Instead of 1 %. are e.g. also 0.5% and 1.5%

desired amounts of the polyacrylate. In some cases it may also be useful to use polyacrylates with higher molecular weights in the specified ranges, e.g. B. 4000-5000, but it is preferred in most cases this range OCE lower part. As in example 1

can make processing easier in some cases

- 61 -

Agent, the perfume, the enzyme, the fluorescent brightener and the pigment can be weighed or replaced, however are in all these cases the specified zeolite, the carbonate, the bicarbonate, the silicate and the bentonite together with the polyacrylate in the specified amounts in the hollow spheres included, as well as the nonionic detergent active ingredient in the final. Detergent compositions that like that other does not contain phosphates.

Ex iel 3

In a pilot plant, hollow spheres were produced for detergent compositions containing 23.37% sodium carbonate, 16.60% sodium carbonate, 34.74% zeolite 4A, 13.64% sodium silicate (Na ₂ OrSiO ratio 1: 2.4) , 0.26% ultramarine blue,

2.20% Tinopal 5BM Extra Cone. (CIBA-Geigy), 1.95% magnesium sulfate 0.32% citric acid (as sodium citrate) 1.29% sodium polyacrylate with a molecular weight of 1000 to 2000 (Alcosperse 107D) and 5.64% moisture. she were prepared by spray drying a pilot crutcher batch containing 50% solids and 50% water, included the water that was added in the aqueous Phosphate solution, with the polyacrylate (if an aqueous solution thereof, such as Alcosperse 107 is used) and with the any Epsom salts used was introduced. The ° other solid components make up the other 50% of the

Crutch mix and are in the same relative amounts present as indicated in relation to the hollow spheres, excluding sodium carbonate and sodium bicarbonate. In these cases, if you get a 1/3 decomposition

of the bicarbonate to carbonate assumes 24.90 parts of sodium bicarbonate (proportionately) and 17.84 parts of sodium carbonate (proportionately) used.

The water introduced into the crutcher consists of deionic

ο

water and has a temperature of 27 C. The added Magnesium sulfate is anhydrous, albeit in its place an equivalent amount of Epsorr salts can be used. After adding the water, the magnesium sulfate will be the Citric acid, Tinopal 5BM Extra Cone., The ultramarine blue

Powder and Alcosperse 107D are added to the crutcher, with the mixer normally running at a relatively slow speed runs. Then the hydrated zeolite 4A (Linde, 20% water of crystallization), the sodium bicarbonate and the sodium carbonate are added, with

the mixer is running at low or medium speed. The mixing speed is then set to a high Adjusted the value and added the sodium silicate as a 47.5% aqueous solution. Mixing up the whole approach continues for about 1 hour (in some cases can

4 hours to be mixed). During this time one goes

noticeable amount of water, sometimes 2 to 6 % lost through evaporation. This water can be replaced if desired. During mixing, the crutcher slurry is constantly agile and there is no gelation, settling, or caking.

As the bicarbonate decomposition depends on the spray drying conditions can vary, the added amounts of bicarbonate and carbonate can also be appropriate can be varied to achieve the desired composition of the hollow spheres to obtain.

About 5 minutes after all components of the Cruther mix were added, the mixture is fed from the crutcher into a pump, which it under a pressure of about 21 kg / cm ^ leads into the upper end of a spray drying tower operated in countercurrent, in which the initial temperature is about 430.degree and the final temperature is about 105 ° C. The hollow spheres formed, consisting essentially of inorganic material have a bulk density of about 0.6 to 0.7 g / ml, low adhesion, particle sizes in a range that is im essentially corresponds to a clear mesh size of 2.00 to 0.149 mm (they are screened out on this area) and have no objectionable amount of fines. The moisture content of the hollow spheres is about

5.6%. The hollow spheres turned out to be free-flowing,
non-sticky, satisfactorily porous, yet of desirable physical strength. You can use slightly increased amounts of e.g. 2 to 5% or stir in liquid

absorb ionic detergent that is sprayed on them without becoming undesirably sticky.

The hollow spheres formed not only have the desired properties, but it has also been found that

the accumulation of product on the inner wall of the spray drying tower is less, often around 20 to 50% less
than when the formulation does not contain any polyacrylate. The throughput speed through the tower is increased and it appears that the content of fines in the product is reduced.

device is. The reduction of accumulations on the tower wall and the formation of fines leads to a much smaller proportion of material to be recycled.

The spray-dried hollow spheres are turned into detergent-20

products are manufactured by spraying a normally waxy, non-ionic detergent, either Neodol 23-6.5, onto the surface of the circulating hollow spheres. or Neodol 23-7 in a heated liquid state in one
such an amount that the finished product contains 20.7% nonionic detergent active ingredient. A proteolytic enzyme

(AlcalaBe) is applied in powder form in such an amount that its concentration in the product is 1.32%. Perfume is sprayed on in an amount that makes its concentration 0.25 % . The detergent obtained has a bulk weight. about 0.7 g / ml and contains 27.0% zeolite (hydrate), 20.7% non-ionic detergent active, 18.17 % sodium carbonate (part of which is formed by decomposition of the sodium bicarbonate), 12.9% sodium bicarbonate, 10 , 6 % sodium silicate, 4.39 % moisture, 1.32 % enzyme, 1.71% fluorescent brightener, 1.51 % magnesium sulfate, 0.25 % citric acid (as citrate), 0.25 % perfume, 0.2% ultramarine Blue and 1.0% sodium polyacrylate. The detergent of this formulation is an excellent heavy duty detergent and is particularly useful for washing household linen in automatic machines

"15 washing machines. It is physically and aesthetically pleasing, since it does not generate dust and flows extremely freely, so that it is confined to glass and plastic bottles Neck can be bottled from which it can be easily dispensed

will.
20th

In comparative tests with similar compositions that no Containing polyacrylate, the compositions according to the invention performed for better dirt and stain removal when different types of dirt and stains appear a variety of test fabrics, including cotton,

β a * Ci C *

- 66 -

Polyester-cotton wiping fabrics, polyester fabrics, and other synthetic fabrics were examined. Regarding
In stain removal, it has often been found that the polyacrylates are often more effective against stains than larger ones

Amounts of the more expensive enzymes which are usually more specific at stain removal and are therefore not as effective for combinations of stains found in many wash fillings. The. Compositions according to the invention containing polyacrylate also have an excellent anti-redeposition action and inhibit soiling of the laundry due to redeposition
removed dirt.

The manufacturing process can be the same as in both

game 1, and various processing agents and auxiliaries can be used as in this one
Example-1 is given. Certain auxiliaries could also be omitted, as also explained in Example 1

is. The mixing temperature in the crutcher can be modified and

ο

z. B. can be increased to 52 C. Also the proportions of the different Components can be varied within the specified ranges by - "10%, -20% and -30%, although they can still be processed Crutch mixes can be obtained leading to the desired Hollow spheres and detergent compositions

to lead. Various compounds can be in aqueous form

Solutions can be added provided the amount of moisture added with them is subtracted from the amount in the crutcher formulation. Other orders of addition can also be used. Zeolites X and Y can be used in place of Zeclith 4A, as well as other types of zeolite A. While the hydrated zeolite 4A of this example is preferably used, various degrees of hydration of the zeolite are acceptable and in some cases nearly anhydrous crystalline zeolites or " ^ O amorphous zeolites can be used. Variierur.g the amount of polyacrylate within the specified range, for example to 1.0 and 1.7% in the hollow spheres still leads to usable products, but the products with a larger proportion of sodium polyacrylate usually have a better effect '* in terms of cleaning, absorption of the nonionic detergent active and improving the spray drying process Usually it is not desirable to use more than about 2% polyacrylate as its effectiveness decreases with higher concentrations and the benefits obtained

I am not economical.

Example 4

A product is made similar to Example 3, but using Alcosperse 107, a sodium

polyacrylate solution in which the polyacrylate has a molecular

- 68 -

. has a weight of about 1COO or 1000 to 2000. It is a clear, amber-colored liquid with a solids content of 30%. The proportion of Alcosperse 107 used is equivalent to the solids content of Alcosperse 107D which was used in Example 1. Instead of Alcosperse 107, solid be -. * · :. Use appropriate amounts of Alcosperse 107 (25% solids) and 149 (40% solids). However, better results are obtained with Alcosperse 107, so that Alcosperse 107 is preferred. In comparison to Example 3, no significant changes were made in the formulation, not even in the process.

The hollow spheres obtained by spray drying the Crutch mix are converted into a finished detergent according to the method described using Neodol 23-6.5 as the nonionic detergent. The product made using Alcosperse 107 is an excellent phosphate-free detergent useful as a heavy duty detergent, effectiveness versus one

* ® possesses wide variety of stains including liquid cosmetic makeup and synthetic sebum (Spangler type). A test group of 10 people strongly preferred such a product over one that did not contain * Alcosperse 107. In a similar way, such a preference was

"Instrument measurements on washed materials are shown.

The described. Tests were carried out on cotton, decron cotton and Nylon Gev. The test conditions included Machine washable using extremely hard water of 150 ppm, a four-step concentration of 0.07% by weight ° and water with a temperature of 49 C.

The same process advantages as in Example 3 observed, including excellent dispersion of the materials in the crutcher and a clean spraying of the product. The hollow spheres have a tearable greater porosity than the control beads without polyacrylate. The bulk weight is no more than a few percent lower, e.g. by 3%, which is concentrated for such Products is important. Similar results will be

Achieved "^ when varying the content of the various other essential components in the formulation by -15% and -30% within OCE specified ranges. These results are also obtained when other types of zeolite A with varying degree of hydration of, for example 15 and 22% and poly-

acrylate rr-it has a molecular weight range from 1000 to 500C be used. Preferably these polyacrylates are neutralized with sodium, either completely or at least at least about 50%. However, it can also be less neutralized

be used.
25th

Results similar to those reported above can be obtained also achieved by using the fluorescent brightener, the perfume, the enzyme and the substances that promote processing (citric acid and magnesium sulphate). In these cases, however, care should be taken to ensure that the spray drying

'5 takes place soon after the crutch mix has been prepared, so that the mixture does not settle in the crutcher. It is clear that the individual properties of the omitted materials get lost, but the product is still a good detergent, the crutch mix is well dispersed.

"^ ⁰ yawed and slightly dried and the hollow spheres have improved porosity.

Example 5

A 4536 kg crutcher batch for making spray-dried

"^ Neter hollow beads containing according to the invention, no water-soluble silicate is obtained by reacting 2132 kg of deionized water having a temperature of about 27 ⁰ C and it initially under low mixing speed 47.2 kg Tinopal 5 BM Extra Cone. ( CIBA-Geigy), 5.9 kg

^ ⁰ Ultramarine blue powder, 3.2 kg sodium polyacrylate (Alcosperse 107D), 957.5 kg hydrated zeolite 4A (linden, 20% crystallization water) 283.5 kg Thixo-Jel No. 1 (bentonite), 714.4 kg sodium bicarbonate ( technical quality), 351.1 kg of sodium carbonate (natural anhydrous soda) and 41.3 kg of titanium dioxide (anatase) in the crutcher. During the

mixing the various components will be the mixing speed increased to a medium value and finally to a high value, and after all ingredients have been added which takes about 15 minutes, mixing will continue for about 1 hour (in some cases 4 5

Mixed for hours). During this time some of the water, e.g. about 90.7 to 272.2 kg, can be evaporated will be lost and, if desired, replaced. During the mixing, the crutcher slurry is steady mobile, and there is no gelation, settling, or caking. Because the bicarbonate during spray drying is partially decomposed to carbonate, the amount of bicarbonate and carbonate in the crutcher formulation can be varied depending on the conditions in the spray drying tower.

Approximately 5 minutes after all of the components have been added to the crutcher mix, the mix is transferred from the crutcher to a

Pump led them under a pressure of about 21 kg / cm

introducing in the upper end of a operated in countercurrent spray tower, in which the initial temperature of about 430 ⁰ C and the final temperature is about 105 ⁰ C. The hollow spheres formed, consisting essentially of inorganic material, have a bulk density of about 0.6 to 0.7 g / ml, an initial adhesion of less than 10% and particle sizes in one

__ Area that essentially has a mesh size of 25th

- 72 - '*

2.00 mm to 0.25 mm (they are screened out on this area), and a fine material fraction that passes through a sieve with a mesh size of 0.297 mm of about 15 %. The moisture content of the hollow spheres is 1 to 10%. The hollow spheres are free-flowing (flow rate 80%), non-sticky, satisfactorily porous, but still have a solid surface and are able to easily absorb substantial parts of liquid nonionic active detergent without becoming undesirably sticky.

Turn detergent out of the spray-dried hollow spheres produced by placing a normally waxy nonionic Active detergent sprayed on. Neodol 23-6.5 is used,

- \ 5 however, Neodol 23-7 or Neodol 25-7 can also be used. The non-ionic active detergent is applied in a heated state at a temperature of about 45 C in such an amount that the end product contains 20 % of the non-ionic active detergent. Proteolytic enzyme (Alcalase) is applied in powder form in an amount such that its concentration in the product is about 1.5%. Furthermore, perfume is sprayed on in an amount such that its concentration is 0.25%. The detergent obtained has a bulk density of about 0.7 to 0.8 g / ml and contains 32.45% zeolite (hydrated), 19.7 % non-ionic detergent, 18.5%

- 73 -

Sodium carbonate (a portion of which is formed by decomposition of the sodium bicarbonate), 13.5% sodium bicarbonate, 1.3% free water, 1.4% enzyme, 1.6% fluorescent brightening agent, 0.25% ^D arfum, 0.2% Ultramarine blue, 9.6% bentonite (Thixo-Jel), 0.1 % sodium polyacrylate and 1.4% titanium dioxide. This detergent is an excellent heavy-duty detergent that is suitable for washing household linen in automatic washing machines. It does not generate dust and is extremely free flowing. It has been found that detergent compositions such as the above bind bentonite containing calcium ions much better, but more importantly, they leave less zeolite residue on laundry washed with them in an automatic washing machine, especially when the laundry is line dried, than comparable compositions that contain less bentonite and sodium silicate in the spray-dried hollow spheres. The difference is particularly pronounced if the washing water is very hard, e.g. contains 200 ppm as calcium carbonate, the washing water is cold and a gentle wash cycle is used.

The manufacturing processes and modifications given in Example 1 can be used and certain auxiliaries as mentioned there omitted. The proportions of the various Components can be within the aforementioned ranges

β tt e * * *

74 -

can be varied by -10%, -20%, and -30%, with editable Crutch mixes obtained will be in the desired Hollow spheres and detergent compositions transferred can be. The solids content in the crutch mix can be varied over the specified range, e.g. B. to 45 and 65%, with good mixing and spray drying is achieved. Instead of zeolite 4A, zeolites X and Y can be used, as well as other zeolite A types. Although the one used in this example is hydrated

^ ⁰ Zeolite 4A preferred, but other degrees of hydration of the zeolite are acceptable and in some cases nearly anhydrous crystalline zeolites or amorphous zeolites can be used. Varying the amount of bentonite within the specified range, for example to 10 and 17%, always leads

"15 still usable products. Those with a larger one However, bentonite content is usually more effective in preventing zeolite from depositing on laundry.

The detergent compositions according to the invention,

containing sparingly soluble silicate or no silicate, improvements achieved in terms of the deposition of less residue on the washed laundry were demonstrated by examining the product described in comparison to a control product which was formulated essentially in the same way, ab.er no bentonite and about 8 % sodium

contained umsilicate. In such an evaluation in a Whirlpool Suds Save model (washing machine was "the washing periods in a gentle cycle were 8 minutes. The detergent concentration was 0.06%, the washing water had a combined calcium-magnesium hardness of 200 ppm as calcium carbonate and the water temperature was 24 C. The following were washed: 100% cotton, 100% polyester, 85 % acetate and 15% nylon as well as 65 % polyester and 35% cotton. The laundry was examined wet and after drying on the line. In both Cases no residue was observed and a moderate residue was observed on all test samples using the control detergent.

The above-described practical test results were confirmed by weighing the residue left on a denim test sample. In this test, the detergent according to the invention is filtered through a sample of the denim material, the detergent being in solution suspension in a concentration of 0.12 % in water with a hardness of 200 ppm (as CaCO) and 24 ° C. The weight of the residue on the fabric is recorded and compared with the value obtained with the control sample. It was found that the residue was only about 75 % compared to the control sample, which is a significant improvement.

- 76 -

In the above adhesion test, with which the stickiness of the Detergent is measured, 10 g of the hollow spheres (or the detergent composition in some cases) evenly placed between two watch glasses, each about 23 cm in diameter. On the top glass a weight of 500 g is placed (both glasses have the concave side facing up). After about 5 minutes If you stand for a long time, the weight is removed from the upper glass and the lower glass is turned over, whereupon you can do this on this glass adhering product weighs. Percent Adhesion is the number of grams of product that will remain on the glass divided by 10 and multiplied by 100.

The flow index is the value that results from a flow test, in which the volumetric flow rates of the Hollow spheres (and in some cases the final product) and of standardized Ottawa sand (-20 +60, U.S. Sieve Series) can be compared by measuring the time it takes for a Complete emptying of a 1.9 l Mason vessel through a hole with a diameter of 2.2 cm in a nozzle on the same Lids are required. The index is the time the sand takes divided by the time the test product needed, expressed as a percentage.

t Λ «■ * J

Example . 6th

The test of Example 5 is repeated on a smaller scale without polyacrylate in the Cruther mixture. The throughput speed through the spray drying tower is noticeably reduced and the absorption capacity of the hollow spheres for the nonionic detergent active is also lower (or the product obtained is somewhat stickier if the same amount of nonionic detergent is used). The crutcher mixture does not solidify in the crutcher, however, the hollow spheres can be produced by spray drying and the detergent formed, although it has a lower content of nonionic detergent active substance of, for example, 17 % in order to achieve flowability and non-adhesive properties, is still a usable product d ar.

Example 7

The process of Example 5 was repeated with 2% sodium silicate with a Na "O: SiO" ratio of 1: 2.4 "which was added to the crutcher as a 47.5% aqueous solution Method of manufacture not gel, however, it is desirable to use magnesium sulfate and citric acid as processing agents to prevent gelation or solidification if the mixture is held in the crutcher longer than normal

will. Also leaves the detergent composition on the washed Wash back more residue, which is more noticeable when the colors of that wash are dark.

Example 8

The procedure of Example 5 was followed with 5% hydrous Nat r iunis i 1 i kat pu 1 ver (Rritesil) repeats the nachträa 1 i was added together with the enzyme powder. This subsequent addition of silica seems to be the zeolite deposit on the -10 washed fabrics do not materially adversely affects the corrosion-preventing effect on the aluminum parts of the washing machine, the water softening and contributes to the builders.

Example 9

The procedure of Example 5 was followed only with water, zeolite, bentonite, sodium carbonate, sodium bicarbonate and sodium polyacrylate repeated in the crutch mixture and in the hollow spheres made from it. Only the applied nonionic detergent. The product obtained has satisfactory cleaning properties, however, it is not commercially acceptable for aesthetic reasons because it does not contain perfume. Nor does it cleanse that way good because of the absence of enzymes and it also does not have the blueing and lightening effects of ultramarine blue and of fluorescent agents in other formulations.

Scha / do

Claims (27)

Claims 1. Free-flowing, spray-dried hollow spheres for the Application of a nonionic detergent active substance for Formation of particulate builder-containing synthetic nonionic organic Detergent products, characterized in that they contain about 15 to 30% by weight of sodium carbonate, about 10 to 22% by weight Wt% sodium bicarbonate, about 10 to 50 wt% water softening aluminum silicate, about 0 to 18 wt.% sodium silicate and about 1 to 20 wt.% bentonite and / or • t · · * ■ about 0.05 to 2 wt.% polyacrylate having a molecular weight from 1000 to 5000 included. 2. Hollow spheres according to claim 1, characterized in that that they contain 15 to 30% by weight of sodium carbonate, 10 to 22% by weight Sodium bicarbonate, 10 to 50% by weight water softener Aluminum silicate, 0 to 18% by weight sodium silicate and 1 to 20% by weight bentonite and / or 0.05 to 2% polyacrylate with a molecular weight of 1000 to 5000 contain. 3. hollow spheres according to claim 2, characterized in that that they contain 0 to 3% by weight of sodium silicate and 1 to 20% by weight of bentonite. 4. hollow spheres according to claim 3, characterized in that 3 that their bulk density is 0.6 to 0.9 g / cm, theirs Particle sizes are in a range corresponding to a clear mesh size of 2.00 mm to 0.149 mm, the aluminum silicate from a hydrated, water-softening sodium zeolite with 15 to 25% by weight of water of hydration and an ion exchange capacity for calcium ions of The sodium silicate consists of 200 to 400 milligram equivalents of calcium carbonate hardness per g of anhydrous zeolite has a NapOiSiOp ratio of 1: 1.4 to 1: 3 and that Sodium carbonate: sodium bicarbonate weight ratio is about 1 to 3. 5. hollow spheres according to claim 4, characterized in that they contain 20 to 30 wt.% Sodium carbonate, 13 to 22 wt.% Sodium bicarbonate, 35 to 45 wt.% Hydrate zeolite, Contains 0% sodium silicate, 5 to 20% by weight bentonite and 1 to 15% by weight water, the water of hydration des Except for zeolites, the zeolite being composed of zeolite A with an outermost mean particle size in the range from 3 to 12 µm and a calcium ion exchange capacity from 250 to 350 milligram equivalents / g as well as a softening speed to a residual hardness of below 0.01 mg / 1 in 10 minutes, the bentonite is a swelling clay with a swelling capacity in water of 3 to 15 ml / g and a viscosity of 3 to 30 centipoise at 6% concentration in water and is the weight ratio Sodium Carbonate: Sodium bicarbonate ranging from 1 to 2 lies. 6. hollow spheres according to claim 5, characterized in that that their bulk density is 0.6 to 0.8 g / cm, they Containing 0.05 to 0.5% by weight of sodium polyacrylate with a molecular weight of 1000 to 5000 and the bentonite from a processed Wyoming bentonite with a swellability from 7 to 15 ml / g and a viscosity of 8 to 30 centipoise at 6% concentration in water consists. -A- 7. hollow spheres according to claim 2, characterized in that that they contain 20 to 40% by weight of water-softening aluminum silicate, 4 to 12% by weight of sodium silicate and 1 to 15% by weight Contains bentonite. 8. hollow spheres according to claim 7, characterized in that they have a bulk density of 0.6 to 0.9 g / cm and particle sizes in the area corresponding to a mesh size of 2.00 mm to 0.149 mm, the aluminum silicate of a hydrated, water-softening zeolite with 15 to 25% by weight of water of hydration and one Ion exchange capacity for calcium ions from 200 to 400 milligram equivalents of calcium carbonate hardness per g of anhydrous zeolite is sodium silicate Na_0: SiOp ratio of 1: 1.4 to 1: 3 and the weight ratio Sodium carbonate: Sodium bicarbonate im Range from about 1 to 3. 9. hollow spheres according to claim 2, characterized in that they contain 20 to 25 wt.% Sodium carbonate, 13 to 19 wt.% Sodium bicarbonate, 30 to 37% by weight hydrated zeolite, Containing 5 to 8% by weight of sodium silicate, 5 to 8% by weight of bentonite and 4 to 10% by weight of water, the water of hydration of the zeolite excepted, the zeolite consists of zeolite A with an outermost mean particle size in the range from 3 to 12 μm, a calcium ion exchange capacity of 250 to 350 milligram equivalents / g and a softening rate to a residual hardness of less than 0.01 mg / 1 in 10 minutes, the sodium silicate a Na _p O: SiOp ratio of 1: 2 to 1: 2.4, the B.entonite from a swelling clay with a swellability in water of 3 to 15 ml / g and a viscosity of 3 to 30 centipoise at 6% concentration in Water and the sodium carbonate: sodium bicarbonate weight ratio is in the range of 1 to 2. 10. hollow spheres according to claim 9, characterized in that 3 that their bulk density is 0.6 to 0.8 g / cm, they 0.1 to 2% by weight of sodium polyacrylate with a molecular weight of 1000 to 5000 and the bentonite made from processed Wyoming bentonite with a swelling capacity of 7 to 15 ml / g and a viscosity of 8 to 30 centipoise at 6% concentration in water, 11. hollow spheres according to claim 2, characterized in that that they contain 20 to 40% by weight of water-softening aluminum silicate, 4 to 18% by weight of sodium silicate and 0.1 to 2% by weight Polyacrylate with a molecular weight of 1000 to 5000 contain. 12. Hollow spheres according to claim 11, characterized in that that they have a bulk density of 0.5 to 0.8 g / cm and particle sizes in the range corresponding to a mesh size of 2.00 to 0.149 mm, the aluminum silicate made of hydrated, water-softening sodium zeolite with 15 to 25 wt.% water of hydration and an ion exchange capacity for calcium ions of 200 to 400 milligram equivalents calcium carbonate hardness per g of anhydrous Zeolite, the sodium silicate has a Na "O: SiOp ratio of 1: 1.4 to 1: 3 and the weight ratio Sodium carbonate: Sodium bicarbonate im Range from about 1 to 3. 13. Hollow spheres according to claim 12, characterized in that they contain 20 to 25% by weight of sodium carbonate, 13 to 19% by weight Sodium bicarbonate, 30 to 37% by weight hydrated zeolite, Contain 7 to 15% by weight of sodium silicate, 0.5 to 1.5% by weight of sodium polyacrylate and 3 to 10% by weight of water, the water of hydration of the zeolite excepted, the zeolite from zeolite A with an outermost middle Particle size from 3 to 12 .mu.m, a calcium nutrient exchangeability from 250 to 350 milligram equ iva] enter; /G and a softening speed to a Pestr.hardness below C. 01 mg / 1 of 10 minutes consists of sodium silicate e'in Ma, -, O ·. Si O, .- Ve r hai tn is before 1: 2 to 1: 2.4 has, ti C. the polyacrylate & υε sodium polyacrylate with a molecular weight from 1000 to 3000 and the weight ratio sodium carbonate: sodium bicarbonate is in the range from 1 to 2. 14. Process for the production of the hollow spheres according to claim 1, characterized in that a Crutchermixture containing 40 to 75% solids according to Claim 1 in an aqueous medium is spray-dried with conversion of part of the sodium bicarbonate into sodium carbonate. 15. The method according to claim 14, characterized in that get a crutch mix that is 50 to 65% solids according to claim 6 in an aqueous medium, spray-dried. 16. The method according to claim 14, characterized in that a crutch mixture which contains 50 to 65% solids according to claim 10 in an aqueous medium, spray-dried. 17. The method according to claim 14, characterized in that one crutch mix of 40 to 70 weight percent solids and 60 to 30% by weight of water, the solids, based on 100%, being about 10 to 25% of sodium carbonate, 15 to 30% of sodium bicarbonate with a sodium carbonate: sodium bicarbonate weight ratio from 0.5 to 2, 20 to 40% of water-softening aluminum silicate, 5 to 18% of sodium silicate and 0.1 to 2% of polyacrylate with a molecular weight of 1000 to 5000, and the Crutchermixture spray dried. 18. Detergent from the hollow spheres according to claim 1, characterized in that the hollow spheres absorb a nonionic detergent active in an amount of Contains 8 to 30% of the detergent. 19. Detergent according to claim 18, characterized in that the nonionic active detergent consists of a condensation product of 6 to 12 moles of ethylene oxide and a higher fatty alcohol with 12 to 16 carbon atoms, the proportion of nonionic active detergent in the detergent is 15 to 22 % and the detergent as well Contains 0.5 to 3% of an enzyme. Ii »* - ♦ · Φ« ι »' 20. Detergent according to claim 18, characterized in that it is made from hollow spheres according to claim 6, which absorb a nonionic detergent active ingredient in an amount of 8 to 25% of the detergent. 21. Detergent according to claim 18, characterized in that it is made from hollow spheres according to claim 8 which absorbs a nonionic detergent active ingredient in an amount 8 to 25% of the detergent. 22. Detergent according to claim 21, characterized in that the nonionic active detergent consists of a condensation product consists of 6 to 12 moles of ethylene oxide and a higher fatty alcohol having 12 to 16 carbon atoms and the detergent also contains 0.5 to 3% of an enzyme. 23. Detergent according to claim 21, characterized in that it is made from hollow spheres according to claim 10, which absorb a nonionic detergent active substance in an amount of 8 to 25% of the detergent. 24. Detergent according to claim 18, characterized in that it contains 13 to 28 wt.% Sodium carbonate, 8 to 18 wt.% Sodium bicarbonate, 15 to 35% by weight water softener Aluminum silicate, 3 to 14% by weight sodium silicate, 0.1 up to 1.6% by weight of polyacrylate with a molecular weight of 1000 to 5000 and 8 to 30% by weight of nonionic detergent active ingredient contains. 25. Detergent according to claim 24, characterized in that 3 that it has a bulk density of 0.6 to 0.9 g / cm and particle sizes in the range corresponding to a mesh size of 2.00 to 0.149 mm, the aluminum silicate consists of hydrated zeolite A with 15 to 25% by weight of water of hydration Sodium silicate a na _? The O: SiO “ratio is from 1: 1.4 to 1: 3, the polyacrylate consists of sodium polyacrylate with a molecular weight of 1000 to 3000, the weight ratio of sodium carbonate: sodium bicarbonate is in the range from 1 to 2, the nonionic detergent is a condensation product from 5 to 12 moles of ethylene oxide and one mole of higher fatty alcohols having 12 to 16 carbon atoms and the composition contains water, excluding the water of hydration of the zeolite, the amount of sodium carbonate 16 to 21%, that of sodium bicarbonate 10 to 15%, that of hydrated Zeolite is 22 to 32 %, that of sodium silicate is 8 to 13%, that of sodium polyacrylate is 0.5 to 1.5%, the moisture content is 3 to 6% and the amount of nonionic detergent active is 10 to 22%. • ft * · ·· «■ - 11 - 26. Crutcher slurry with improved miscibility and pumpability for the production of the hollow spheres according to claim 1, characterized in that it contains 40 to 70% by weight of solids and 60 to 30% by weight of water, the solids, based on 100%, being too ' about 10 to 25% from sodium carbonate, from 15 to 30 % from sodium bicarbonate with a weight ratio of sodium bicarbonate: sodium carbonate of 0.5 to 2, to 20 to 40% from water-softening aluminum silicate, to 4 to 18 % from sodium silicate and to 0, 1 to 2% consist of polyacrylate with a molecular weight of 1000 to 5000. 27. Crutcher slurry according to claim 26, characterized in that it is on an anhydrous basis 1.5 to 2.5 % magnesium sulfate, 0.2 to 0.5% sodium citrate, 0.2 to 0.4% ultramarine blue, 1.5 to Contains 3% fluorescent brightener and 0.5 to 1.5% sodium polyacrylate with a molecular weight of 1000 to 3000.